Low Resistance State Research Articles

Power efficient MoS2 synaptic devices based on Maxwell–Wagner interfacial charging in binary oxides

Synaptic devices with tunable weight hold great promise in enabling non-von Neumann architecture for energy efficient computing. However, conventional metal-insulator-metal based two-terminal memristors share the same physical channel for both programming and reading, therefore the programming power consumption is dependent on the synaptic resistance states and can be particularly high when the memristor is in the low resistance states. Three terminal synaptic transistors, on the other hand, allow synchronous programming and reading and have been shown to possess excellent reliability. Here we present a binary oxide based three-terminal MoS2 synaptic device, in which the channel conductance can be modulated by interfacial charges generated at the oxide interface driven by Maxwell-Wagner instability. The binary oxide stack serves both as an interfacial charge host and gate dielectrics. Both excitatory and inhibitory behaviors are experimentally realized, and the presynaptic potential polarity can be effectively controlled by engineering the oxide stacking sequence, which is a unique feature compared with existing charge-trap based synaptic devices and provides a new tuning knob for controlling synaptic device characteristics. By adopting a three-terminal transistor structure, the programming channel and reading channel are physically separated and the programming power consumption can be kept constantly low (∼50 pW) across a wide dynamic range of 105. This work demonstrates a complementary metal oxide semiconductor compatible approach to build power efficient synaptic devices for artificial intelligence applications.

RF-wave induced CBRAM characteristic modulation specific to sheet-like conductive filaments

The shape of conductive filaments in CBRAM is important for resistance switching and conductance modulation, especially in applications like neuromorphic and reservoir computing that use conductance as weight. We report on RF-induced modulation of CBRAM using Ge2Sb3.4Te6.2 with sheet-like filaments and compared it to those with dendritic filaments. RF input below 100 MHz reduced SET and RESET voltages, similar to CBRAM with dendritic filaments, but showed significantly different resistance changes. Repeated RF on/off input gradually increased the resistance of low-resistance state, unlike the dendritic filament CBRAM, where the resistance decreased. The increased resistance suggests RF-induced denser sheet-like filaments. Furthermore, the resistance of the high-resistance state showed a peculiar RF-induced resistance change not observed in dendritic filaments. The resistance decreased during RF input and increased to nine times the initial value when RF was switched off. The results show that the conductance modulation by RF input strongly depends on the filament type.

Resistive switching behaviour of nickel nanoparticle-embedded naphthalene sulphonic acid-doped polyaniline nanocomposites

Hybrid nanocomposite (NC) materials comprising organic polymers and inorganic metal nanoparticles (NPs) with unique properties are popular for their advanced technological applications including resistive switching memory devices. Herein, NCs of 2-naphthalene sulphonic acid-doped polyaniline nanotubes (PANI-NSA NTs) and nickel nanoparticles (Ni NPs) were synthesized via a facile chemical synthesis procedure where metallic Ni NPs were embedded in/deposited onto the surface of PANI-NSA NTs by a simple reduction method. Different characterization methods revealed successful deposition of weak ferromagnetic Ni NPs onto the PANI-NSA matrix. The bipolar resistive switching behaviour of the as-synthesized PANI-NSA + Ni NCs was investigated under the application of voltage stress in a two-terminal sandwiched device configuration. The fabricated indium tin oxide/PANI-NSA + Ni/silver (ITO/PANI-NSA + Ni/Ag) device displays bipolar resistive switching properties having a memory window of ∼1.5 × 103, and switches effectively over 200 cycles. Ohmic conduction in the lower-voltage regime and the space-charge-limited Mott–Gurney current conduction model in the higher-voltage region were identified as major charge conduction mechanisms in the high resistive state of the device. On the other hand, in the entire low resistive state region the experimental data followed the Mott–Gurney conduction model.

Improved oxygen ion migration efficiency and resistive switching properties in SrFeOx memristor with vertical superlattice-like structure

The resistive switching (RS) behaviour between high and low resistance states in SrFeOx memristors originates from topological phase transition (TPT) induced by the migration of oxygen ions. Accelerating the migration of oxygen ions in the anisotropic crystal structure of SrFeO2.5 is of great importance for improving the RS properties and promoting the application for this TPT memristor. In this study, SrFeOx TPT memristors with different superlattice-like (SLL) structures were fabricated and the prepared devices with a vertical-type SIL structure display an ultra-low operation voltage of only 0.6 V, excellent cycling stability, data retention, and endurance performance. Moreover, the microstructures of vertical and horizontal SLL SrFeO2.5 were characterized with X-ray diffraction and transmission electron microscope. Furthermore, the differences in oxygen ion migration rate in the two structures were also tested by in-situ X-ray photoelectron spectroscopy. Finally, the optical band gaps and oxygen ion migration barriers of the two structures were calculated using first principles. All the characterizations and simulation results prove that the vertical type SrFeOx shows a higher oxygen ion migration efficiency. More encouragingly, the vertical SLL devices exhibit up to 96 % recognition accuracy for the Mixed National Institute of Standards and Technology image recognition task.

High-performance resistive random access memory using two-dimensional electron gas electrode and its switching mechanism analysis

In this study, a two-dimensional electron gas (2DEG), which is a conductive layer formed at the interface of Al2O3 and TiO2, was used as an electrode for resistive random access memory (RRAM) and implemented in a cell size down to 30 nm. For an RRAM device comprising W/2DEG/TiO2/W, we confirmed that the dominant switching mechanism changed from interfacial to filamentary as the cell size decreased from 500 nm to 30 nm. Through analyses of changes in forming characteristics and conduction mechanisms in the low resistive state depending on the cell size, it was identified that the 2DEG acted as an oxygen-scavenging layer of TiO2 during the resistive switching process. By comparing the switching characteristics of RRAM devices with and without 2DEG for a 30 nm cell size, we confirmed that a high-performance 2DEG RRAM was realized, with highly uniform current–voltage characteristics, a low operating voltage (∼1 V), and a high on/off ratio (>102). Finally, the applicability of the proposed device to a crossbar array was validated by evaluating 1S1R operation with an NbO2-based selector. Considering the improved switching uniformity, the 2DEG RRAM shows promise for high-density memory applications.

Ag-dispersive chalcogenide media for readily activated electronic memristor

In this paper, we report a Ag-dispersive chalcogenide thin film as a resistance-switching material for memristive devices. The memristive device with Ag/Ge2Se3Te5/W showed an initial low resistance state in its pristine stage (electro-forming-free), a low power consumption of 60 nW, robust state retention in a harsh environment of 85 °C for 2 h, and reliable endurance. We used high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, Auger electron spectroscopy, and electrical conduction characteristics to determine the microscopic origin of the memristive device. Comparative studies of different electrodes and resistive switching layers indicated that the diffusive Ag atom in the chalcogenide thin film plays a crucial role in realizing distinctive memristive characteristics. Further, we highlighted that the observed favorable performance of the memristive device is possible with a chalcogenide material, which can serve as an electrolyte for high ion diffusion and desirable electronic traps. Moreover, the memristive device exhibited an analogous conductance variation in a nonvolatile manner, which can be adopted as an artificial synaptic device. Based on the observed synaptic performance, an inference accuracy of ∼92% was achieved using handwritten numbers from the Modified National Institute of Standards and Technology database.

Coexistence of Electrochromism and Bipolar Nonvolatile Memory in a Single Viologen.

Viologens are fascinating redox-active organic compounds that have been widely explored in electrochromic devices (ECDs). However, the combination of electrochromic and resistive random-access memory in a single viologen remains unexplored. We report the coexistence of bistate electrochromic and single-resistor (1R) memory functions in a novel viologen. A high-performance electrochromic function is achieved by combining viologen (BzV2+2PF6) with polythiophene (P3HT), enabling a "push-pull" electronic effect due to the efficient intermolecular charge transfer in response to an applied bias. The ECDs show high coloration efficiency (ca. 1150 ± 10 cm2 C-1), subsecond switching time, good cycle stability (>103 switching cycles), and low-bias operation (±1.5 V). The ECDs require low power for switching the color states (55 μW cm-2 for magenta and 141 μW cm-2 for blue color). The random-access memory devices (p+2-Si/BzV2+2PF6/Al) exhibit distinct low and high resistive states with an ON/OFF ratio of ∼103, bipolar and nonvolatile characteristics that manifest good performances, and "Write"-"Read"-"Erase" (WRE) functions. The charge conduction mechanism of the RRAM device is elucidated by the Poole-Frenkel model where SET and RESET states arise at a low transition voltage (VT = ±1.7 V). Device statistics and performance parameters for both electrochromic and memory devices are compared with the literature data. Our findings on electrochromism and nonvolatile memory originated in the same viologen could boost the development of multifunctional, smart, wearable, flexible, and low-cost optoelectronic devices.

Research on electronic synaptic simulation of HfO2-based memristor by embedding Al2O3

The potential of neuromorphic computing in synaptic simulation has led to a renewed interest in memristor. However, the demand for multilevel resistive switching with high reliability and low power consumption is still a great resistance in this application. In this work, the electronic synaptic plasticity and simulated bipolar switching behavior of Pt/Al2O3(2 nm)/HfO2 (10 nm)/Al2O3 (2 nm)/Ti tri-layer memristor is investigated. The effect of Al2O3 layer embedded at the top electrode and the bottom electrode on the resistive performance of the memristor was studied. It is found that both of them can effectively improve the reliability of the device (104 cycles), the resistive window (>103), the tunable synaptic linearity and reduce of the operating voltage. RRAM with Al2O3 embedded at the top electrode have higher uniformity and LTP linearity, while those with Al2O3 embedded at the bottom electrode significantly reduce the operating current (∼10 μA) and improve LTD linearity. Electron transport mechanisms were compared between single-layer HfO2 and tri-layer Al2O3/HfO2/Al2O3 samples under DC scanning. The results showed that the thin Al2O3 layer at the top electrode led to Fowler Northeim tunneling in the low-resistance state, while the thin Al2O3 layer at the bottom electrode led to Schottky emission in the high-resistance state. The Al2O3/HfO2/Al2O3 memristors were successfully used to achieve synaptic properties, including enhancement, inhibition, and spike time-dependent plasticity, demonstrating an important role in high-performance neuromorphic computing applications.

The Memristive Properties and Spike Timing-Dependent Plasticity in Electrodeposited Copper Tungstates and Molybdates.

Memristors possess non-volatile memory, adjusting their electrical resistance to the current that flows through them and allowing switching between high and low conducting states. This technology could find applications in fields such as IT, consumer electronics, computing, sensors, and medicine. In this paper, we report successful electrodeposition of thin-film materials consisting of copper tungstate and copper molybdate (CuWO4 and Cu3Mo2O9), which showed notable memristive properties. Material characterisation was performed with techniques such as XRD, XPS, and SEM. The electrodeposited materials exhibited the ability to switch between low and high resistive states during varied cyclic scans and short-term impulses. The retention time of these switched states was also explored. Using these materials, the effects seen in biological systems, specifically spike timing-dependent plasticity, were simulated, being based on analogue operation of the memristors to achieve multiple conductivity states. Bio-inspired simulations performed directly on the material could possibly offer energy and time savings for classical computations. Memristors could be crucial for the advancement of high-efficiency, low-energy neuromorphic electronic devices and technologies in the future.

Resistive switching characteristics of MnO2-based thin film for transparent non-volatile ReRAM

The present study covers the fabrication of indium tin oxide (ITO)/manganese dioxide (MnO2)/ITO capacitor-based transparent resistive random access memory (ReRAM) device. The ITO/MnO2/ITO device exhibits 80 % transparency in the visible region along with steady bipolar resistive switching characteristics. The conduction mechanism investigation reveals that the current in low resistance state (LRS) is governed by Ohmic conduction. However, the dominance of trap-controlled space charge limited conduction (SCLC) mechanism in high resistance state (HRS) was observed. The resistive switching phenomenon in ITO/MnO2/ITO device was caused due to the formation and rupture of conduction filament via electron trapping and de-trapping in oxide-related traps (oxygen vacancies). In terms of reliability, the MnO2-based device exhibits good endurance up to 104 cycles and long retention for 104 s at room-temperature as well as at 85 °C. Cumulative probability distribution shows resistance ratio of 103 between LRS and HRS, which is sufficient to read memory states. These outcomes suggest that the ITO/MnO2/ITO-based transparent ReRAM could be a futuristic see-through electronic device for artificial intelligence (AI) application.

Temperature Dependence of Electrical Properties and Conduction Mechanism of SiNx‐Based Resistive Random Access Memory

Herein, the effect of temperature on the switching characteristics and the conduction mechanism of the Ti/SiNx/Pt resistive random access memory device is investigated. The switching behavior of the device is investigated by comparing the I–V curves of the device in the temperature range of RT‐653 K. The temperature dependence of the current and the conduction mechanism of the device within RT‐463 K is investigated. It is found that the device exhibits good bipolar switching behavior in the temperature range of RT‐463 K, and the low resistance state (LRS) current and high resistance state (HRS) current show an increasing and then decreasing trend with increasing temperature. There is a stronger temperature dependence of the LRS current and the conduction mechanism from ohmic conduction to Schottky emission under LRS, which is attributed to the involvement of the reactive electrode Ti in the reaction at a certain temperature and the generation of a TiNx layer. Based on the above phenomenon, it is believed that not only the temperature affects the reliability of the device, but also the influence of reactive electrodes cannot be ignored. This article provides a reference for further preparation of SiNx‐based resistive random access memory devices with higher reliability and wider temperature usage range.

Estimation of the activation energy in the Ag/SnSe/Ge2Se3/W self-directed channel memristor

In this study, we conducted an investigation into the Ag/SnSe/Ge2Se3/W ionic memristor, focusing on the determination of activation energies associated with its two primary operational processes: the formation of conductive filaments and memristor degradation. To ascertain the electrical conductivity of the memristor in both its basic electronic states, a low resistance state and a high resistance state, we constructed current-voltage characteristics. The estimation of activation energy values was carried out employing the Arrhenius law and the provisions of irreversible thermodynamics, with specific reference to Onsager's second postulate. This fundamental concept posits that the growth rate of irreversible component of entropy can be expressed as the summation of products involving fluxes and thermodynamic forces when a system tends towards its equilibrium state. In the context of this study, the equilibrium state of the memristor is defined as the condition at which the memristor can no longer function as a resistive memory cell. Our experimentation involved the application of a flux of Ag+ ions (electromigration). The calculated activation energy values were found to be 0.24 eV for the initial process and 1.16 eV for the latter. These divergent activation energy values indicate the differentiation between the agglomerative mechanism that governs the formation of conductive channels, prevalent in the Ag/SnSe/Ge2Se3/W memristor, and the "conventional" substance transfer mechanism based on a group of point defects that manifests itself during the memristor's degradation.

Correlation between Electronic Structure, Microstructure, and Switching Mode in Valence Change Mechanism Al2O3/TiOx‐Based Memristive Devices

AbstractMemristive devices with valence change mechanism (VCM) show promise for neuromorphic data processing, although emulation of synaptic behavior with analog weight updates remains a challenge. Standard filamentary and area‐dependent resistive switching exhibit characteristic differences in the transition from the high to low resistance state, which is either abrupt with inherently high variability or gradual and allows quasi‐analog operation. In this study, the two switching modes are clearly correlated to differences in the microstructure and electronic structure for Pt/Al2O3/TiOx/Cr/Pt devices made from amorphous layers of 1.2 nm Al2O3 and 7 nm TiOx by atomic layer deposition. For the filamentary mode, operando spectromicroscopy experiments identify a localized region of ≈50 nm in diameter of reduced titania surrounded by crystalline rutile‐like TiO2, highlighting the importance of Joule heating for this mode. In contrast, both oxide layers remain in their amorphous state for the interfacial mode, which proves that device temperature during switching stays below 670 K, which is the TiO2 crystallization temperature. The analysis of the electronic conduction behavior confirms that the interfacial switching occurs by modulating the effective tunnel barrier width due to accumulation and depletion of oxygen vacancies at the Al2O3/TiOx interface. The results are transferable to other bilayer stacks.

Mixed‐Halide Perovskite Memristors with Gate‐Tunable Functions Operating at Low‐Switching Electric Fields

AbstractCrossbar circuits based on two terminal (2T) memristors typically require an additional unit such as a transistor for individual node selection. A memristive device with gate‐tunable synaptic functionalities will not only integrate selection functionality at the cell level but can also lead to enriched on‐demand learning schemes. Here, a three‐terminal (3T) mixed‐halide perovskite memristive device with gate‐tunable synaptic functions operating at low potentials is demonstrated. The device operation is controlled by both the drain (VD) and gate (VG) potentials, with an extended endurance of >2000 cycles and a state retention of >5000 s. Applying a voltage (Vset) of 20 V across the 50 µm channel switches its conductance from a high‐resistance state (HRS) to a low‐resistance state (LRS). A memristive switching mechanism is proposed that is supported by current injection models through a Schottky barrier and Kelvin probe force microscopy data. The simultaneous application of a VG potential is found to further modulate the channel conductance and reduce the operating Vset to 2 V, thus requiring a low electric field of 400 V cm−1, which is by a factor of 50× less compared to state‐of‐the‐art literature reports. Gate‐tunable retention, endurance, and synaptic functionalities are demonstrated, further highlighting the beneficial effect of VG on device operation.

Influences of Cu Doping on the Microstructure, Optical and Resistance Switching Properties of Zinc OxideThin Films.

Copper-doped zinc oxide films (Zn1-xCuxO) (x = 0, 2%, 4%, 6%) were fabricated on conductive substrates using the sol-gel process. The crystal structure, optical and resistive switching properties of Zn1-xCuxO films are studied and discussed. RRAM is made using Zn1-xCuxO as the resistive layer. The results show that the (002) peak intensity and grain size of Zn1-xCuxOfilms increase from 0 to 6%. In addition, PL spectroscopy shows that the oxygen vacancy defect density of Zn1-xCuxO films also increases with the increase in Cu. The improved resistive switching performance of the RRAM device can be attributed to the formation of conductive filaments and the destruction of more oxygen vacancies in the Zn1-xCuxO film. Consequently, the RRAM device exhibits a higher low resistance state to high resistance state ratio and an HRS state of higher resistance value.

Effect of Annealing on Resistive Switching Properties of Glancing Angle Deposition‐Assisted WO3 Thin Films

Herein, the impact of postdeposition annealing on resistive switching behavior of radio frequency magnetron sputtered WO3 thin films is reported. Films are deposited under glancing angle deposition (GLAD) configuration of sputtering at varying GLAD angle from 65° to 80°. Structure transition from monoclinic to orthorhombic phase in deposited WO3 films is perceived after ex situ annealing at temperature of 400 °C. Resistive switching properties show shift from bipolar to unipolar switching on postdeposition annealing. WO3 films show unipolar switching behavior after ex situ annealing for all prepared samples. The value of resistance in high resistance state is lowered after ex situ heating treatment and interestingly switching voltage also reduces to 3 V from 7 V after annealing treatment. The ratio of high to low resistance state for annealed WO3 film fabricated at 70° GLAD angle is achieved to be maximum (≈219). A detailed charge transport mechanism shows that ohmic behavior is dominant current conduction mechanism at lower applied voltage, while space charge limited current and Child's law are dominant at higher applied voltages. Obtained results encourage utilization of prepared WO3 thin films toward a wide variety of applications in optoelectronics, microelectronics, and environmental engineering along with advanced electronics such as resistive memory devices.

The effect of Cr atoms: From non-stoichiometric Ge-Te to Cr2Ge2Te6

The traditional phase change material Ge-Te presents a large difference with Cr2Ge2Te6 (CrGT) in the phase change properties. Compared with Ge-Te, the two-dimensional van der Waals material CrGT presents a reversed resistance state, in which the crystalline phase is in a high-resistance state and the amorphous phase is in a low-resistance state. Nevertheless, there are some structural similarities between the two materials. CrGT may be regarded as the Cr doping of Ge-Te. It is necessary to investigate the evolution of the structure and phase change properties of Ge-Te to CrGT through Cr doping. In this study, phase change materials Ge40Te60 (GT) and CrGT were fabricated. Subsequently, a series of intermediate state films were fabricated by changing the Ge/Te/Cr cation-to-anion ratio. Surprisingly, the coexistence of the CrGT and GT phases was observed in all intermediate films. As a result, a gradual reversal in the resistance between the amorphous and crystalline states can be observed. Transmission electron microscopy experiments were also performed to characterize the grain growth and the phase separation. Unlike GT, CrGT island-like crystal grains usually have boundaries with regular shapes. The pure CrGT-based device exhibited an excellent device performance. This work may provide a useful guide for further application of the CrGT phase change material.

Study of the doping of PEDOT:PSS films and the reversibility in organic electrochemical transistors

In this work, the effect in the performance of organic electrochemical transistors (OECTs) due to the doping with a secondary dopant solvent of poly(3,4ethylenedioxythiophene): poly (styrene sulfonic acid) (PEDOT:PSS) films) has been studied. We found an improvement in the performance of the OECTs related to the increase of conductivity of the PEDOT:PSS film due to the doping with ethylene glycol (EG). We found that PEDOT:PSS films doped with EG showed higher conductivity due to the improvement of conducting paths between the PEDOT+ chains, which causes a higher transconductance and response of the OECTs. However, a higher concentration of EG is detrimental to the OECT performance due to the removal of PSS- chains caused by the EG secondary doping, which was corroborated by X-ray diffraction.We propose that the good reversibility between low-resistance state (ON) to high-resistance state (OFF), is caused by the injection/removal of cations in the polymeric film to maintain the electroneutrality. We found applying more negative gate voltage pulses in the transfer characteristics of the OECTs is necessary to reach the complete oxidation of the PEDOT:PSS film, as lower negative voltages only partially dedope the film.

Non-volatile resistive switching behavior and time series analysis of Ag/PVA-graphene oxide/Ag device

Non-volatile memory devices have been getting significant attention from researchers worldwide in recent years due to their application in resistive random access memory and neuromorphic computing. Here, we have fabricated polyvinyl alcohol-graphene oxide (PVA-GO) composite as an active material for the resistive switching with different concentrations of GO (0.0, 0.1, 0.2, 0.3, 0.4, and 0.5 wt. % GO solution) dispersed in 5 wt. % PVA matrix in a 2:1 volume ratio. We demonstrate the non-volatile forming free resistive switching properties of Ag/PVA-GO/Ag devices. Structural properties of PVA-GO composites are established from the x-ray diffraction pattern, which indicates the complete dispersion of GO inside the PVA matrix. The Ag/PVA-GO-0.1 wt. %/Ag device shows better bipolar resistive switching at VSET ∼ 0.4 V and VRESET at ∼−0.8 V. This device indicates well-resolved two distinct states at a read voltage of 0.1 V in endurance and retention measurements. The fabricated device switches successfully tested for 2.5 × 103 cycles and retains its state for 3.36 × 103 s without any observable degradation. Furthermore, the non-volatile retention property was modeled using time series analysis. For this, Holt–Winter's exponential smoothing technique was utilized. Additionally, the charge–flux linkage characteristic shows the double-valued function, and time domain–charge and time domain–flux show asymmetric behaviors. The electrical conduction mechanism exhibits ohmic behavior in the entire region of the low resistance state and the lower voltage region of the high resistance state. In the high-voltage region of the high resistance state, the space charge-limited conduction mechanism is observed. The resistive switching behavior is explained with the help of an appropriate model.

Performance Enhancement and In Situ Observation of Resistive Switching and Magnetic Modulation by a Tunable Two‐Level System of Mn Dopants in a‐Gallium Oxide‐based Memristor

AbstractPurely gallium oxide‐based memristors (GOMRs) show great potentials in resistive random‐access‐memory (RRAM) due to their chemical stability and resistive switching characteristics with Roff/Ron ratios up to 102; indeed, GOMRs with higher Roff/Ron ratios and more functionalities are more expected. In this study, ferromagnetic amorphous gallium oxide (a‐GMO) films with a tunable two‐level system of Mn dopants, i.e., Mn2+ and Mn3+ ions, are prepared by scalable polymer assisted deposition. The Pt/a‐GMO/Pt memristors show a high Roff/Ron ratio of 103, at least one order of magnitude higher than those of previously reported purely GOMRs, thanks to the abundant oxygen vacancies (VOs)‐induced low resistance state and Mn2+‐enhanced high resistance state. Meanwhile, magnetic modulation (MM) is realized electrically in the a‐GOMRs during the RS, through the tuning of bound magnetopolarons (BMPs) by bias voltage‐induced VOs variations, which may be useful for quaternary information coding. Notably, the transition between Mn3+ and Mn2+ions is observed in the GOMRs, which is closely related to the variations of VO concentration and BMP amount, providing an in situ tool to probe the VO‐induced RS and BMP‐dependent MM. The results give insights to Mn‐doped GOMRs and may be useful for design, fabrication, and testing of multifunctional high‐performance RRAMs.