Impact of Bi Deficiencies on Ferroelectric Resistive Switching Characteristics Observed at p‐Type Schottky‐Like Pt/Bi1–δFeO3 Interfaces

This work reports a resistive switching effect observed at rectifying Pt/Bi_1–δFeO₃ interfaces and the impact of Bi deficiencies on its characteristics. Since Bi deficiencies provide hole carriers in BiFeO₃, Bi‐deficient Bi_1–δFeO₃ films act as a p‐type semiconductor. As the Bi deficiency increased, a leakage current at Pt/Bi_1–δFeO₃ interfaces tended to increase, and finally, rectifying and hysteretic current–voltage (I–V) characteristics were observed. In I–V characteristics measured at a voltage‐sweep frequency of 1 kHz, positive and negative current peaks originating from ferroelectric displacement current were observed under forward and reverse bias prior to set and reset switching processes, respectively, suggesting that polarization reversal is involved in the resistive switching effect. The resistive switching measurements in a pulse‐voltage mode revealed that the switching speed and switching ratio can be improved by controlling the Bi deficiency. The resistive switching devices showed endurance of >10⁵ cycles and data retention of >10⁵ s at room temperature. Moreover, unlike conventional resistive switching devices made of metal oxides, no forming process is needed to obtain a stable resistive switching effect in the ferroelectric resistive switching devices. These results demonstrate promising prospects for application of the ferroelectric resistive switching effect at Pt/Bi_1–δFeO₃ interfaces to nonvolatile memory.     

Thermally Stable Transparent Resistive Random Access Memory based on All‐Oxide Heterostructures

An all‐oxide transparent resistive random access memory (T‐RRAM) device based on hafnium oxide (HfO_x) storage layer and indium‐tin oxide (ITO) electrodes is fabricated in this work. The memory device demonstrates not only good optical transmittance but also a forming‐free bipolar resistive switching behavior with room‐temperature R_OFF/R_ON ratio of 45, excellent endurance of ≈5 × 10⁷ cycles and long retention time over 10⁶ s. More importantly, the HfO_x based RRAM carries great ability of anti‐thermal shock over a wide temperature range of 10 K to 490 K, and the high R_OFF/R_ON ratio of ≈40 can be well maintained under extreme working conditions. The field‐induced electrochemical formation and rupture of the robust metal‐rich conductive filaments in the mixed‐structure hafnium oxide film are found to be responsible for the excellent resistance switching of the T‐RRAM devices. The present all‐oxide devices are of great potential for future thermally stable transparent electronic applications.     

缺陷相互作用对HfO2基阻变存储器件均匀性的影响：第一性原理研究

The physical mechanism of doping effects on switching uniformity and operation voltage in Al-doped HfO₂ resistive random access memory（RRAM） devices is proposed from another perspective:defects interactions, based on first principle calculations.In doped HfO₂,dopant is proved to have a localized effect on the formation of defects and the interactions between them.In addition,both effects cause oxygen vacancies（V_O） to have a tendency to form clusters and these clusters are easy to form around the dopant.It is proved that this process can improve the performance of material through projected density of states（PDOS） analysis.For V_O filament-type RRAM devices, these clusters are concluded to be helpful for the controllability of the switching process in which oxygen vacancy filaments form and break.Therefore,improved uniformity and operation voltage of Al-doped HfjO₂ RRAM devices is achieved.     

Study of radiation hardness of HfO2-based resistive switching memory at nanoscale by conductive atomic force microscopy

A resistive switching random access memory (RRAM) with an HfO₂/Ti structure grown on a molybdenum (MO) substrate was fabricated, and a gold (Au) conductive atomic force microscopy (CAFM) tip was used as the top electrode such that the cell area of the resulting RRAM device is as small as 3 × 10⁻¹² cm². The pre- and post-irradiated resistive switching behaviors of the RRAM device with various HfO₂ layer thicknesses were investigated after being subjected to Co⁶⁰ γ-ray irradiation with different radiation doses. It is found that the forming voltage (V_forming), set voltage (V_set), resistance of high resistance state (RHRS) and resistance of low resistance state (RLRS) of the RRAM device are all radiation dose-dependent. The V_forming, V_set, RHRS and RLRS all decrease as the radiation dose increases due to increasing radiation-induced oxygen vacancies or defects inside the HfO₂ layer. Our experimental results indicate that the HfO₂-based RRAM cell with an extremely small cell area is not actually radiation hard since the operating voltage will change with V_forming and V_set after irradiation.     

Resistive Random Access Memory Cells with a Bilayer TiO2/SiOX Insulating Stack for Simultaneous Filamentary and Distributed Resistive Switching

In order to fulfill the information storage needs of modern societies, the performance of electronic nonvolatile memories (NVMs) should be continuously improved. In the past few years, resistive random access memories (RRAM) have raised as one of the most promising technologies for future information storage due to their excellent performance and easy fabrication. In this work, a novel strategy is presented to further extend the performance of RRAMs. By using only cheap and industry friendly materials (Ti, TiO₂, SiO_X, and n⁺⁺Si), memory cells are developed that show both filamentary and distributed resistive switching simultaneously (i.e., in the same I–V curve). The devices exhibit unprecedented hysteretic I–V characteristics, high current on/off ratios up to ≈5 orders of magnitude, ultra low currents in high resistive state and low resistive state (100 pA and 125 nA at –0.1 V, respectively), sharp switching transitions, good cycle‐to‐cycle endurance (>1000 cycles), and low device‐to‐device variability. We are not aware of any other resistive switching memory exhibiting such characteristics, which may open the door for the development of advanced NVMs combining the advantages of filamentary and distributed resistive switching mechanisms.     

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.     

Light-Mediated Multi-Level Flexible Copper Iodide Resistive Random Access Memory for Forming-Free,Ultra-Low Power Data Storage Application

This study demonstrates the efficacy of an emerging p-type copper iodide (CuI) semiconductor in a flexible, low-voltage resistive random-access memory (RRAM), which can be readily integrated with metal-oxide n-type counterparts for complementary circuit systems. Herein, CuI RRAM devices are implemented via a room-temperature solid iodination process, exhibiting a consistent On/Off ratio (≈10⁴), excellent endurance of more than ≈10³ cycles, together with a long retention period (> 5 × 10⁴ s). Furthermore, a scheme of light-mediated multi-level data storage is demonstrated using blue light illumination (λ = 455 nm), to exploit possible photonic memristive functionality through notable photo-response of CuI. In addition, the current conduction and resistive switching behaviors are systematically studied via low-temperature measurements from 203 to 343 K, validating thermal stability and the governing key switching mechanism in CuI RRAM devices. The longstanding problem with CuI device longevity is effectively addressed via PMMA encapsulation, resulting in a 15-fold improvement in the lifespan of devices even in air, as compared with non-passivated devices. These findings suggest that flexible optoelectronic systems, combined with reliable, ultra-low power CuI RRAM devices with photo memristive functionality, can leverage the enhancement of multifunctional selectors required in process-in-memories and the synaptic elements of neuromorphic applications.     

Electric-pulse-induced resistive switching and possible superconductivity in the Mott insulator GaTa4Se8

There is accumulated evidence today that an electric pulse can drastically modify the physical properties of correlated materials. An electric pulse was shown for example to induce an insulator-to-metal transition in manganites or in organic Mott insulators. We report here the first experimental evidence of a non-volatile electric pulse-induced insulator-to-metal transition and possible superconductivity in the Mott insulator GaTa₄Se₈. This resistive switching is concomitant to an electronic phase separation induced by the pulse. This phenomena most probably differs from the thermal, electronic injection or ionic diffusion processes explaining the resistive switching in materials foreseen for non-volatile memory (RRAM) applications.     

Submillimeter 2D Bi2Se3 Flakes toward High‐Performance Infrared Photodetection at Optical Communication Wavelength

Infrared detection at optical communication wavelength is of great significance because of their diverse commercial and military communication applications. The layered Bi₂Se₃ with a narrow band gap of 0.3 eV is regarded as a promising candidate toward high‐performance terahertz to infrared applications. However, the controllable synthesis of large‐size ultrathin Bi₂Se₃ flakes remains a challenge owing to complex nucleation process and infrared telecommunication photodetectors based on Bi₂Se₃ flakes are rarely reported. Here, large size (submillimeter: 0.2–0.4 mm in lateral dimensions) and ultrathin (thickness: 3 nm to few nanometers) 2D Bi₂Se₃ flakes with high crystal quality are obtained by suppressing the nucleation density. More importantly, back‐gate field‐effect transistor based on Bi₂Se₃ flake exhibits an ultrahigh on/off current ratio of 10⁶ and competitive mobility of 39.4 cm² V^?1 s^?1. Moreover, excellent on/off ratio of 972.5, responsivity of 23.8 A W^?1, and external quantum efficiency of 2035% are obtained from Bi₂Se₃‐based photodetector at 1456 nm in the E‐band of the telecommunication range. With controlled morphology and excellent photoresponse performance, the Bi₂Se₃ photodetector shows great potential in the optoelectronic field including communications, military, and remote sensing.     

A journey towards reliability improvement of TiO2 based Resistive Random Access Memory: A review

A Resistive Random Access Memory (RRAM), where the memory performance principally originated from ‘resistive’ change rather than ‘capacitive’ one (the case with conventional CMOS memory devices), has attracted researchers across the globe, owing to its unique features and advantages meeting the demands of future generation high-speed, ultra low power, nano dimensional memory devices. A large family of semiconducting oxides have been investigated as insulator for Resistive Random Access Memory (RRAM), amongst which TiO₂ is one of the potential candidate, principally owing to some of its remarkable advantages e.g. wide band gap, high temperature stability and high dielectric constant with flexibility to offer both unipolar and bipolar switching, which are essential for RRAM device applications. In this review article, we tried to represent the long voyage of TiO₂ based RRAM, towards the improvement of the reliability aspects of the device performance in a comprehensive manner. Starting with the key factors like oxygen vacancies, Ti interstitials and electroforming, which are responsible for resistive switching phenomenon, various material preparation techniques for RRAM development have been discussed with emphasis on relative merits and bottlenecks of the process. The factors like electrode material and geometry, device structuring, doping, compliance current, annealing effect etc., which play the pivotal role in determining the switching performance of the device, have been reviewed critically. Finally, the article concludes with the comparison of different TiO₂ based RRAM devices followed by the prediction of possible future research trends.     

Resistive switching characteristics of CMOS embedded HfO2-based 1T1R cells

This work addresses a 1T1R RRAM architecture, which allows for the precise and reliable control of the forming/set current by using an access transistor. The 1T1R devices were fabricated in a modified 0.25 μm CMOS technology. The memory cells show stable resistive switching in dc as well as pulse-induced mode with an endurance of 10³ and 10² cycles, respectively. The variation of pulse widths as a function of amplitudes in 1R devices confirmed the set process distribution over a wide range of pulse widths (300 ns-100 μA), whereas the reset process variation is confined (1-3 μs).     

Low power resistive switching memory using Cu metallic filament in Ge0.2Se0.8 solid-electrolyte

Bipolar resistive switching memory device using Cu metallic filament in Au/Cu/Ge_0.2Se_0.8/W memory device structure has been investigated. This resistive memory device has the suitable threshold voltage of V_th > 0.18 V, good resistance ratio (R_High/R_Low) of 2.6 × 10³, good endurance of >10⁴ cycles with a programming current of 0.3 mA/0.8 mA, and 5 h of retention time at low compliance current of 10 nA. The low resistance state (R_Low) of the memory device decreases with increasing the compliance current from 1 nA to 500 μA for different device sizes from 0.2 μm to 4 μm. The memory device can work at very low compliance current of 1 nA, which can be applicable for extremely low power-consuming memory devices.     

2D Metal–Organic Framework Nanosheets with Time‐Dependent and Multilevel Memristive Switching

Metal–organic framework (MOF) nanosheets have attracted significant interests for sensing, electrochemical, and catalytic applications. Most significantly, 2D MOF with highly accessible sites on the surface is expected to be applicable in data storage. Here, the memory device is first demonstrated by employing M‐TCPP (TCPP: tetrakis(4‐carboxyphenyl)porphyrin, M: metal) as resistive switching (RS) layer. The as‐fabricated resistive random access memory (RRAM) devices exhibit a typical electroforming free bipolar switching characteristic with on/off ratio of 10³, superior retention, and reliability performance. Furthermore, the time‐dependent RS behaviors under constant voltage stress of 2D M‐TCPP–based RRAMs are systematically investigated. The properties of the percolated conducting paths are revealed by the Weibull distribution by collecting the measured turn‐on time. The multilevel information storage state can be gotten by setting a series of compliance current. The charge trapping assisted hopping is proposed as operation principle of the MOF‐based RRAMs which is further confirmed by atomic force microscopy at electrical modes. The research is highly relevant for practical operation of 2D MOF nanosheet–based RRAM, since the time widths, magnitudes of pulses, and multilevel‐data storage can be potentially set.     

Ultrahigh Stability 3D TI Bi2Se3/MoO3 Thin Film Heterojunction Infrared Photodetector at Optical Communication Waveband

Infrared (IR) detection at 1300–1650 nm (optical communication waveband) is of great significance due to its wide range of applications in commerce and military. Three dimensional (3D) topological insulator (TI) Bi₂Se₃ is considered a promising candidate toward high‐performance IR applications. Nevertheless, the IR devices based on Bi₂Se₃ thin films are rarely reported. Here, a 3D TI Bi₂Se₃/MoO₃ thin film heterojunction photodetector is shown that possesses ultrahigh responsivity (R_i), external quantum efficiency (EQE), and detectivity (D*) in the broadband spectrum (405–1550 nm). The highest on–off ratio of the optimized device can reach up to 5.32 × 10⁴. R_i, D*, and the EQE can reach 1.6 × 10⁴ A W^?1, 5.79 × 10¹¹ cm² Hz^1/2 W^?1, and 4.9 × 10⁴% (@ 405 nm), respectively. Surprisingly, the R_i can achieve 2.61 × 10³ A W^?1 at an optical communication wavelength (@ 1310 nm) with a fast response time (63 µs), which is two orders of magnitude faster than that of other TIs‐based devices. In addition, the device demonstrates brilliant long‐term (>100 days) environmental stability under environmental conditions without any protective measures. Excellent device photoelectric properties illustrate that the 3D TI/inorganic heterojunction is an appropriate way for manufacturing high‐performance photodetectors in the optical communication, military, and imaging fields.     

Thickness effect on the bipolar switching mechanism for nonvolatile resistive memory devices based on CeO2 thin films

Impact of switching layer thickness on the bipolar resistive memory performance, stability and uniformity has been investigated in Ti/CeO₂/Pt devices. XRD and FTIR analyses demonstrate polycrystalline nature of CeO₂ films and the formation of a TiO interface layer. The bipolar switching characteristics like HRS and LRS dispersion are found to be dependent on the thickness of CeO₂ layer. As it is noted that forming as well as SET voltages gradually increase with increasing CeO₂ layer thickness however RESET voltages are slightly affected. Oxygen gettering ability of Ti causes the formation of TiO layer, which not only extracts oxygen ions from the ceria film but also acts as ion reservoir, hence plays a key role in stable functioning of the memory devices. Current transport behavior is based upon Ohmic and interface modified space charge limited conduction. Based on unique distribution characteristics of oxygen vacancies in CeO₂ films, a possible mechanism of resistive switching in CeO₂ RRAM devices has been discussed.     

Resistive random access memory and its applications in storage and nonvolatile logic

The resistive random access memory (RRAM) device has been widely studied due to its excellent memory characteristics and great application potential in different fields. In this paper, resistive switching materials, switching mechanism, and memory characteristics of RRAM are discussed. Recent research progress of RRAM in high-density storage and nonvolatile logic application are addressed. Technological trends are also discussed.     

The resistive switching characteristics of a Ti/Gd2O3/Pt RRAM device

We successfully fabricated the Gd₂O₃ film for the application of resistive random access memory (RRAM). The resistive switching behavior of the Ti/Gd₂O₃/Pt capacitor structure could be both operated under positive or negative bias. However, there was a significant difference on the switching properties. The switching behavior under positive bias operation was more stable, had less voltage and resistance fluctuation, and had longer endurance than that of the negative one. We propose that the anode electrode plays an important role in the switching characteristics and may be the cause of the asymmetry of the I-V curves between positive and negative operation.     

Bipolar resistive switching of chromium oxide for resistive random access memory

This study investigates the resistance switching characteristics of Cr₂O₃-based resistance random access memory (RRAM) with Pt/Cr₂O₃/TiN and Pt/Cr₂O₃/Pt structures. Only devices with Pt/Cr₂O₃/TiN structure exhibit bipolar switching behavior after the forming process because TiN was able to work as an effective oxygen reservoir but Pt was not. Oxygen migration between Cr₂O₃ and TiN was observed clearly before and after resistance switching from Auger electron spectroscopy (AES) analysis. Both low resistance state, ON state, and high resistance state, OFF state, of Pt/Cr₂O₃/TiN structures are stable and reproducible during a successive resistive switching. The resistance ratio of ON and OFF state is over 10², on top of that, the retention properties of both states are very stable after 10⁴ s with a voltage of −0.2 V.     

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.     

Compliance current dominates evolution of NiSi2 defect size in Ni/dielectric/Si RRAM devices

Resistive random access memory (RRAM) devices with a nickel top electrode form controllable metal nanofilaments and have robust resistive switching performance. We investigate the Ni/HfO₂/SiO_x/n⁺ Si RRAM structure, which forms a Ni-rich defect in the silicon underneath the Ni nanofilament in the dielectric layers after a SET process. The formation of these defects may affect the retention of the devices, so we applied a detailed Finite Element Method and Kinetic Monte Carlo approach to simulate the Ni-rich defect evolution under different compliance current settings. We confirm that the chemical composition of the defects is metallic NiSi₂, and that their size is determined by the compliance current. These simulation results are supported by in-situ STM-like experiments inside a transmission electron microscope (TEM). NiSi₂ defects are shaped as truncated square pyramids, and we show that this is due to the low activation energy of Ni migration along the (111) crystal plane of Si. Our results demonstrate that electromigration is the main driving force for Ni migration initially, after which thermal migration and especially stress migration become the dominant mechanism. This work gives a fascinating example of an as-grown metal–insulator–semiconductor (MIS) system that can be controllably converted to a metal–insulator–metal (MIM) configuration for down-scaled RRAM operation.