Resistive Switching Behavior Research Articles

A Novel Strategy to Construct Metal–Organic Frameworks‐Based Memristor with Enhanced Proton Conduction

The limited conductivity of metal‐organic frameworks (MOFs) poses a significant challenge to their application in the domain of memristors. The proton conduction capabilities of MOFs can be improved through the incorporation of guest molecules. Herein, hydrogen protons are introduced into MIL‐53 (Al) via acid leaching, which not only enhances the proton conductivity of MIL‐53 (Al) but also contributes to its superior resistance switching behavior. The results indicate that untreated MIL‐53 (Al) exhibits negligible resistance switching behavior; however, following hydrochloric acid leaching, it demonstrates excellent retention (103 cycles), longtime durability (103 s), and a favorable ON/OFF ratio (≈25) under bias conditions. Furthermore, under suitable pulse stimulation, the MIL‐53 (Al)‐based memristor successfully emulates biological synaptic behaviors, including excitatory postsynaptic current and paired pulse facilitation. This research presents a novel approach for enhancing the resistive switching performance of MOF‐based memristors.

Investigation of resistive switching behavior driven by active and passive electrodes in MoO2–MoS2 core shell nanowire memristors

Memristive devices based on layered materials have the potential to enable low power electronics with ultra-fast operations toward the development of next generation memory and computing technologies. Memristor performance and switching behavior crucially depend on the switching matrix and on the type of electrodes used. In this work, we investigate the effect of different electrodes in 1D MoO2–MoS2 core shell nanowire memristors by highlighting their role in achieving distinct switching behavior. Analog and digital resistive switching are realized with carbon based passive (multi-layer graphene and multiwall carbon nanotube) and 3D active metal (silver and nickel) electrodes, respectively. Temperature dependent electrical transport studies of the conducting filament down to cryogenic temperatures reveal its semiconducting and metallic nature for passive and active top electrodes, respectively. These investigations shed light on the physics of the filament formation and provide a knob to design and develop the memristors with specific switching characteristics for desired end uses.

Coexistence of analog and digital resistive switching behaviors in TiN/SiNx resistive random access memory device

The digital–analog hybrid resistive random access memory can not only be used in computing in memory integrated circuits but also adapt to various requirements, such as achieving lower integration complexity. In this work, resistive memory devices with Ta/SiNx/TiN/Pt structures were fabricated, which exhibit a gradual analog or abrupt digital resistive state (DRS) characteristic depending on the different applied voltage range. The experimental results indicate that different RS switching of these devices is due to the change in the conductive mechanism in the SiNx/TiN double-layer structure. The Schottky barrier at the SiNx/TiN interface is the cause of analog resistive state characteristics under low sweeping voltage, while the formation/rupture of the conductive filaments formed under large voltage is the reason for the device to exhibit DRS characteristics.

Effect of annealing conditions on resistive switching in hafnium oxide-based MIM devices for low-power RRAM

Abstract This work presents resistive switching (RS) behaviour in HfO2-based low-power resistive random-access memory (RRAM) devices. A metal-insulator-metal (MIM) structure (Au/HfO2/Pt) was fabricated by sandwiching a thin insulating layer of HfO2 between Pt and Au electrodes. HfO2 films deposited by RF sputtering at room temperature were rapid thermally annealed in N2 ambient at 400 °C and 500 °C. Grazing angle x-ray diffraction (GIXRD), Field emission gun-scanning electron microscopy (FEG-SEM), atomic force microscopy (AFM), and x-ray photoelectron spectroscopy (XPS) were employed to analyse the phase, crystal structure, morphology, surface roughness and chemical composition of the HfO2 films. The bipolar RS could be observed in both as-deposited and annealed HfO2 film-based devices from I–V characteristics measured using a source meter. We have investigated the effect of annealing temperature and annealing ambient on the phase formation of HfO2 as well as the RS characteristics and compared with as-deposited film-based device. Annealed HfO2 film-based devices exhibited improved electrical characteristics, including stable and repeatable RS at significantly lower switching voltages (<1 V) which indicates low power consumption in these devices. The relatively lower processing temperature of the HfO2 films and that too in the films deposited by physical vapor deposition (PVD) technique-RF magnetron sputtering makes this study significantly useful for resistive switching based non-volatile memories.

A semiconducting supramolecular Co(II)-metallogel based resistive random access memory (RRAM) design with good endurance capabilities.

A highly efficient approach for synthesizing a supramolecular metallogel of Co(II) ions, denoted as CoA-TA, has been established under room temperature and atmospheric pressure conditions. This method employs the metal-coordinating organic ligand benzene-1,3,5-tricarboxylic acid as a low molecular weight gelator (LMWG) in DMF solvent. A comprehensive analysis of the mechanical properties of the resulting supramolecular Co(II)-metallogel was conducted through rheological investigation, considering angular frequency and thixotropic study. The hierarchical rocky network structure of the supramolecular Co(II)-metallogel was unveiled using field emission scanning electron microscopy (FESEM). Transmission electron microscopic (TEM) analysis showed rod-shaped structures via low-magnification high angle annular dark field (HAADF) bright field scanning transmission electron microscopic (STEM) imaging, while energy dispersive X-ray (EDX) elemental mapping confirmed its primary chemical constituents. The formation mechanism of the metallogel was examined via fourier transform infrared spectroscopy (FTIR) spectroscopy. The nature of the synthesized CoA-TA metallogel was affirmed through powder X-ray diffraction (PXRD) analysis. Furthermore, this study involved fabrication of Schottky diode structures in a metal-semiconductor-metal geometry based on cobalt(II) metallogel (CoA-TA), enabling observation of charge transport behavior. Remarkably, a resistive random access memory (RRAM) device utilizing cobalt(II) metallohydrogel (CoA-TA) demonstrated bipolar resistive switching at room temperature and under ambient conditions. The switching mechanism was investigated, revealing the formation and rupture of conductive filaments between metal electrodes that govern the resistive switching behavior. This RRAM device exhibited an impressive ON/OFF ratio (~ 414) and exceptional endurance over 5000 switching cycles. These structures offer great potential for diverse applications such as non-volatile memory design, neuromorphic computing, flexible electronics and optoelectronics. Their advantages lie in their fabrication process, reliable resistive switching behavior and overall performance stability.

Proton‐Modulated Resistive Switching in a Synapse‐Like Tyrosine‐Rich Peptide‐Based Memristor

AbstractArtificial intelligence has become an essential part of the daily lives and has revolutionized various sectors, including healthcare, finance, transportation, and entertainment. With a substantial increase in processed data, neuromorphic devices that replicate the operation of the human brain have been emphasized owing to their superior efficiency. Typical neuromorphic devices focus on constructing synapse‐like structures. However, biological synapses have more complex mechanisms for efficient data processing. One of the most prominent mechanisms is proton activation, which forms an ion concentration gradient prior to the transmission of neurotransmitters and plays a key role in efficient computation. In this study, proton‐mediated signaling at biological synapses is successfully replicated by fabricating a proton‐modulated memristor device using a tyrosine‐rich peptide film. The ionic input of the memristor is controlled by applying a voltage to proton‐permeable PdHx contacts in a hydrogen atmosphere, thus successfully adjusting the resistive switching behavior. Remarkable improvements in resistive switching and computing performance are observed through proton injection, analogous to “proton‐mediated signaling” at the actual synapse. It is believed that this study proposes a new paradigm for designing biorealistic devices and provides inspiration for precisely controllable ion‐based neuromorphic devices.

A diffusive memristor with two dimensional ZrCl2

Layered transition metal halides have been identified as potential materials for memristors due to their distinctive structure and exceptional electrical properties. However, systematic studies on their preparation processes and properties have been scarce in recent years. This study marks a significant milestone as it successfully synthesizes two-dimensional layered ZrCl2 nanomaterials using chemical vapor deposition techniques. Subsequently, an Ag/ZrCl2/Au diffusion memristor was fabricated utilizing the synthesized ZrCl2 material, followed by comprehensive performance evaluations. The results demonstrate that under DC voltage conditions, the memristor exhibits stable abrupt resistive switching behavior, with a high resistance state to low resistance state ratio reaching up to 103; this stability persists even after 9×104 cycles. Furthermore, after approximately 1000 operating cycles, the memristor displays gradual resistance switching behavior characterized by continuous changes in its resistance value corresponding to variations in voltage levels. Notably, this study successfully emulates key features of biological nociceptors such as "threshold," "no adaptation," and "plasticity." A proposed mechanism based on silver ion migration elucidates the observed resistance switching phenomenon. These research findings underscore broad application prospects for 2D transition metal halides within the realm of memristors, while also offering a novel approach towards developing high-performance and long-life neuromorphic computing devices.

Resistive switching behaviors and conduction mechanisms of IGZO/ZnO bilayer heterostructure memristors

Resistive switching behaviors and conduction mechanisms of IGZO/ZnO bilayer heterostructure memristors

Influence of rapid thermal annealing in vacuum on the resistive switching of Cu/ZnO/ITO devices

In this paper, we investigate the resistive switching (RS) behavior of Cu/ZnO/ITO devices subjected to various rapid thermal annealing (RTA) temperatures under vacuum. Current–voltage characteristics reveal that following the application of a positive electroforming voltage, both unannealed ZnO films and those annealed at 200 °C exhibit bipolar RS, consistent with the electrochemical metallization mechanism (ECM). However, films annealed at higher temperatures exhibit RS with both positive and negative electroforming threshold voltages and coexistence of switching in both polarities. Ultimately, these films display RS behavior aligned with the valence change mechanism (VCM), dominated by a negative electroforming voltage and RS on the negative bias side, while positive electroforming voltage and RS vanish for films annealed at 600 °C. Curve fitting analysis was conducted for Schottky emission (SE), space-charge limited current, and Poole–Frenkel (PF) emission mechanisms, with SE and PF emission providing better fits. These results demonstrate the tunability of ECM and VCM RS modes and the polarity of the forming bias, underscoring the potential of vacuum RTA in advancing ZnO-based memory device development.

Synaptic Properties of an Interfacial Memristor Based on a Ga2O3/Nb:SrTiO3 Heterojunction.

Memristors have been extensively studied for tremendous potential for future neuromorphic computing hardware applications because of their ability to imitate biological synaptic processes. Herein, we report an interfacial memristor based on a Ga2O3/Nb:SrTiO3 heterojunction that shows stable bipolar resistive switching behavior, long retention time, and high switching ratio. The conductance of the Au/Ga2O3/Nb:SrTiO3/In memristor can be gradually modulated under the voltage sweep mode as well as positive and negative pulse voltage stimulations, respectively, thus realizing the long-term potentiation/depression characteristics of the simulated biological synapse. A neural network based on the prepared memristor was built to recognize the handwritten picture data set with a recognition accuracy of 92.78% by using the NeuroSimV3.0 platform. Our work indicates that the Ga2O3/Nb:SrTiO3 heterojunction memristor has significant potential in a neuromorphic computing system.

Role of sulphur in resistive switching behavior of natural rubber-based memory

The rising environmental awareness has spurred the extensive use of green materials in electronic applications, with bio-organic materials emerging as attractive alternatives to inorganic and organic materials due to their natural biocompatibility, biodegradability, and eco-friendliness. This study showcases the natural rubber based resistive switching memory devices and how varying sulphur concentrations (0 - 0.8 wt.%) in natural rubber thin films impact the resistive switching characteristics. The natural rubber was formulated and processed into a thin film deposited on an ITO substrate as the bottom electrode and with an Ag film as the top electrode. The addition of sulphur modifies the degree of crosslinking in the natural rubber thin film, from which the concentration of -C=C- group and density of defect site (S+) are affected, and hence the resistive switching behavior of the memory device. The devices exhibit bipolar resistance with symmetric switching characteristics which are attributed to the formation of conductive paths facilitate by electron transport along -C=C- and S+ defect sites between the two electrodes. Notably, a sample with 0.2 wt.% sulphur exhibits a high ON/OFF ratio (104), a large memory window (5.5 V), prolonged data retention (10 years), and reliable endurance (120 cycles). These findings highlight the potential of natural rubber as a promising material for eco-friendly resistive-switching random access memory applications.&#xD.

Control of ferroelectricity in Ta-doped HfO2 and its non-zero-crossing current–voltage hysteresis behavior

Hafnium oxide (HfO2)-based ferroelectrics are being explored as potential candidates for ferroelectric memory devices due to their highly compatibility with complementary metal-oxide-semiconductor (CMOS) technology. Enhancing the remanent polarization and investigating the underlying mechanism are crucial tasks. In the present study, tantalum (Ta) was introduced as a dopant to induce ferroelectric properties in HfO2, a large portion of orthorhombic phase was recognized in the as-grown Ta:HfO2 without further thermal treatment. The remanent polarization of Ta:HfO2 thin films can be optimized by adjusting the oxygen flow rates during the sputtering process. The influencing factors for enhanced ferroelectric performance include the control of Ta concentration, its valence state, and the presence of singly ionized oxygen vacancies, which are influenced by oxygen addition. Furthermore, the resistive switching behavior showing non-zero crossing current–voltage (I–V) hysteresis is associated with ferroelectricity and the presence of oxygen vacancies. A model has been proposed to explain the ferroelectric resistive switching with non-zero crossing I–V characteristics by considering the role of oxygen vacancies and polarization effects. This model suggests that the oxygen vacancies at the surface layer, along with ferroelectric polarization, play a crucial role in electron transport.

The Fabrication of Polyimide-Based Tunable Charge Traps Ternary Memristors Doped with Ni-Co Coated Carbon Composite Nanofibers.

In the dynamic fields of information science and electronic technology, there is a notable trend towards leveraging carbon materials, favored for their ease of synthesis, biocompatibility, and abundance. This trend is particularly evident in the development of memristors, benefiting from the unique electronic properties of carbon to enhance device performance. This study utilizes sensitized chemical evaporation and spin-coating carbonization techniques to fabricate nickel-cobalt coated carbon composite nanofibers (SC-NCMNTs). Novel polyimide (PI) matrix composite memory devices were fabricated using in situ polymerization technology. Transmission electron microscopy (TEM) and micro-Raman spectroscopy analyses validated the presence of dual interface structures located between the Ni-Co-MWNTs, carbon composite nanofibers, and PI matrix, revealing a significant number of defects within the SC-NCMNTs/PI composite films. Consequently, this results in a tunable charge trap-based ternary resistive switching behavior of the composite memory devices, exhibiting a high ON/OFF current ratio of 104 and a retention time of 2500 s at an operating voltage of less than 3 V. The mechanism of resistive switching is thoroughly elucidated through a comprehensive charge transport model, incorporating molecular orbital energy levels. This study provides valuable insights for the rational design and fabrication of efficient memristors characterized by multilevel resistive switching states.

Bipolar resistive switching behavior of bilayer β-Ga2O3/WO3 thin film memristor device

This article investigates the bipolar resistive switching behavior of bilayer Au/β-Ga2O3/WO3 thin film (TF)/Ag heterostructure memristor device deposited using an electron beam evaporation technique. The purity of the deposited sample was confirmed by the XRD and FESEM with EDS characterizations. The root mean square roughness(RRMS) of single layer WO3 TF and heterolayer of Ga2O3/WO3 TF were obtained from the AFM analysis as 4.56 nm and 2.20 nm, respectively. The presence of more oxygen vacancies in WO3 sample was also confirmed by the XPS analysis. The optical measurement of the sample also revealed a bandgap of ∼ 4.35 eV for β-Ga2O3 TF and ∼ 3.66 eV for WO3 TF. Moreover, the bilayer Au/β-Ga2O3/WO3 TF/Ag heterostructure memristor device demonstrated bipolar resistive switching behavior with a good resistance ratio of ∼ 182, an endurance of 300 cycles, and a data retention of 103 s at room temperature. The device also yielded a low SET power of 1.17 mW (at 1.74 mA, +0.67 V) and a low RESET power of 2.50 mW (at 7.16 mA, – 0.35 V). The logarithmic current-voltage (I-V) relationship revealed that the switching behavior of the memristor device is mainly dominated by Ohmic conduction in LRS as well as Child’s square law, TCLC and Ohmic conductions in HRS. With the above parameters, the Au/β-Ga2O3/WO3 TF/Ag memristor device has the potential for future RRAM applications.

Large resistive switching in ultrathin BiFeO3 thin films

Electrically induced resistive switching (RS) effects have been proposed as the basis for future non-volatile memories. In this work, 9 nm-thick BiFeO3 (BFO) epitaxial thin films were deposited on (001)-oriented SrTiO3 substrates by pulsed laser deposition and their resistive switching (RS) behaviors were investigated. A large resistive switching with ON/OFF ratio of ∼106 is observed, surpassing the performance of most resistive random access memories ever reported. The conducting filament is proposed to dominate the RS behavior in the positive voltage region, while the modulation of ferroelectric polarization is suggested to play a significant role in the negative voltage region. Our study significantly deepens the understanding of the physical origin of RS and could provide a reference for designing high-performance memories and memristors based on ultrathin ferroelectric films.

A multilevel resistive switching memristor based on flexible organic–inorganic hybrid film with recognition function

Abstract Brain-inspired neuromorphic computing systems fueled the emergence of memristor-based artificial synapses, however, conventional silicon-based devices restricted their usage in the wearable field because of their difficulty in bending. To tackle the above challenge, a vertically structured flexible memristor with aluminum-based hydroquinone organic–inorganic hybrid film and Al2O3 as the functional layer, ITO and Pt as the bottom and top electrodes, and PET as the substrate has been developed utilizing molecular/atomic layer deposition to achieve a tradeoff between the resistive transition properties and the flexibility of memristors. The obtained devices combine stable resistive switching behavior and flexibility, showing high switching ratio of 103, better retention (up to 105 s) and endurance properties (up to 104 cycles), and robustness at radius of curvature of 4.5 mm after 104 bending cycles. Furthermore, the presence of multilevel resistive states in these devices ensures that the memristor can emulate synaptic properties such as paired-pulse facilitation, transition from short-term plasticity to long-term plasticity, long-term potentiation and depression, and spike-time-dependent plasticity. The resistive switching mechanism and the role of the bending state on the electrical performance of the device are explored. The fully connected artificial neural network based on the memristor can achieve a recognition accuracy of 90.2% for handwritten digits after training and learning. Flexible memristor will bring feasible advances to the integration of neuromorphic computing and wearable functionality.

Synergetic engineering of oxidizable, redox, and inert metal decorated copper oxide for non-volatile memory and neuromorphic computing applications

Abstract In the quest for efficient resistive switching (RS) materials for both non-volatile memory and neuromorphic computing applications, a variety of functional materials have been researched in the last few years. Herein, we systematically synthesized Ni, Ag, and Au decorated copper oxide (CuxO) by using an electrochemical approach and investigated their RS performance for both non-volatile memory storage and neuromorphic computing applications. By tuning various electrochemical parameters, we optimized Ni, Ag, and Au decoration over the CuxO switching layers to understand the effect of oxidizable, redox, and inert metal decoration, respectively. Fabricated Ni-CuxO/FTO, Ag-CuxO/FTO, and Au-CuxO/FTO devices show forming-free bipolar and analog properties of RS behavior. The electrical measurements asserted that the electrodeposited Ni-CuxO/FTO RS device shows excellent RS, non-volatile memory, and synaptic learning properties compared to the Ag-CuxO/FTO, and Au-CuxO/FTO devices. Moreover, the statistical and Weibull distribution parameters suggested that the Ni-CuxO/FTO RS device has lower switching variation than the other two devices. The conduction mechanisms of all devices are investigated by fitting the appropriate physics-oriented models. It was found that Ohmic and Child's square law were dominated during the charge transport and the RS process occurred due to the filamentary switching effect. Results suggested the electro-decorated/-deposited Ni-CuxO is a suitable switching layer for memory as well as neuromorphic computing applications.

The Role of Hydrogen in ReRAM.

Previous research on transistor gate oxides reveals a clear link between hydrogen content and oxide breakdown. This has implications for redox-based resistive random access memory (ReRAM) devices, which exploit soft, reversible, dielectric breakdown, as hydrogen is often not considered in modeling or measured experimentally. Here quantitative measurements, corroborated across multiple techniques are reported, that reveal ReRAM devices, whether manufactured in a university setting or research foundry, contain concentrations of hydrogen at levels likely to impact resistance switching behavior. To the knowledge this is the first empirical measurement depth profiling hydrogen concentration through a ReRAM device. Applying a recently-developed Secondary Ion Mass Spectrometry analysis technique enables to measure hydrogen diffusion across the interfaces of SiOx ReRAM devices as a result of operation. These techniques can be applied to a broad range of devices to further understand ReRAM operation. Careful control of temperatures, precursors, and exposure to ambient during fabrication should limit hydrogen concentration. Additionally, using thin oxynitride or TiO2 capping layers should prevent diffusion of hydrogen and other contaminants into devices during operation. Applying these principles to ReRAM devices will enable considerable, informed, improvements in performance.

Analog‐Digital Hybridity of Resistive Switching in Ion‐Irradiated BiFeO3 Memristor for Synergistic Neuromorphic Functionality and Artificial Learning

AbstractMemristors‐based neuromorphic devices represent emerging computing architectures to perform complex tasks by outpacing the traditional Von‐Neumann architectures in terms of speed, and energy efficiency. In this work, the resistive switching (RS) behavior of sol‐gel grown and ion‐irradiated BFO films is investigated under electrical stimulus. The Ag/BFO/FTO memristors emulate a combination of digital and analog RS behavior within a single device. The possible mechanism of analog digital hybridity is addressed by considering the formation of the conducting filament by oxygen vacancies, Ag+ ions and Schottky barrier height modulation. The ion‐irradiated BFO samples are analyzed using the Raman, XRD, and XPS studies. To uphold bioinspired synaptic actions, crucial synaptic functionalities like pair‐pulse facilitation and long‐term potentiation/depression are effectively achieved. More intricate synaptic behaviors are also demonstrated such as spike‐time‐dependent plasticity and Pavlovian classical conditioning, which represent the prominent attributes of both learning and forgetting behavior. Additionally, high pattern recognition accuracy (96.1%) is achieved in an artificial neural network simulation by using the synaptic weights of the memristors. This synergistic effect of digital and analog RS in ion‐irradiated BFO can be beneficial for the emulation of complex learning behavior as well as its incorporation into low‐power neuromorphic computing.

Effect of SiCN thin film interlayer for ZnO-based RRAM.

This study investigates the effect of silicon carbon nitride (SiCN) as an interlayer for ZnO-based resistive random access memory (RRAM). SiCN was deposited using plasma-enhanced chemical vapor deposition (PECVD) with controlled carbon content, achieved by varying the partial pressure of tetramethylsilane (4MS). Our results indicate that increasing the carbon concentration enhances the endurance of RRAM devices but reduces the on/off ratio. Devices with SiCN exhibited lower operating voltages and more uniform resistive switching behavior. Oxygen migration from ZnO to SiCN is examined by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses, promoting the formation of conductive filaments (CFs) and lowering set voltages. Additionally, we examined the impact of top electrode oxidation on RRAM performance. The oxidation of the Ti top electrode was found to reduce endurance and increase low resistive state (LRS) resistance, potentially leading to device failure through the formation of an insulating layer between the electrode and resistive switching material. The oxygen storage capability of SiCN was further confirmed through high-temperature stress tests, demonstrating its potential as an oxygen reservoir. Devices with a 20 nm SiCN interlayer showed significantly improved endurance, with over 500 switching cycles, compared to 62 cycles in those with a 5 nm SiCN layer. However, the thicker SiCN layer resulted in a notably lower on/off ratio due to reduced capacitance. These findings suggest that SiCN interlayers can effectively enhance the performance and endurance of ZnO-based RRAM devices by acting as an oxygen reservoir and mitigating the top electrode oxidation effect.