Control of Switching Modes and Conductance Quantization in Oxygen Engineered HfOx based Memristive Devices

Hafnium oxide (HfO_x)‐based memristive devices have tremendous potential as nonvolatile resistive random access memory (RRAM) and in neuromorphic electronics. Despite its seemingly simple two‐terminal structure, a myriad of RRAM devices reported in the rapidly growing literature exhibit rather complex resistive switching behaviors. Using Pt/HfO_x/TiN‐based metal–insulator–metal structures as model systems, it is shown that a well‐controlled oxygen stoichiometry governs the filament formation and the occurrence of multiple switching modes. The oxygen vacancy concentration is found to be the key factor in manipulating the balance between electric field and Joule heating during formation, rupture (reset), and reformation (set) of the conductive filaments in the dielectric. In addition, the engineering of oxygen vacancies stabilizes atomic size filament constrictions exhibiting integer and half‐integer conductance quantization at room temperature during set and reset. Identifying the materials conditions of different switching modes and conductance quantization contributes to a unified switching model correlating structural and functional properties of RRAM materials. The possibility to engineer the oxygen stoichiometry in HfO_x will allow creating quantum point contacts with multiple conductance quanta as a first step toward multilevel memristive quantum devices.     

Realization of the Switching Mechanism in Resistance Random Access Memory™ Devices: Structural and Electronic Properties Affecting Electron Conductivity in a Hafnium Oxide–Electrode System Through First-Principles Calculations

The resistance random access memory (RRAM?) device, with its electrically induced nanoscale resistive switching capacity, has attracted considerable attention as a future nonvolatile memory device. Here, we propose a mechanism of switching based on an oxygen vacancy migration-driven change in the electronic properties of the transition-metal oxide film stimulated by set pulse voltages. We used density functional theory-based calculations to account for the effect of oxygen vacancies and their migration on the electronic properties of HfO₂ and Ta/HfO₂ systems, thereby providing a complete explanation of the RRAM? switching mechanism. Furthermore, computational results on the activation energy barrier for oxygen vacancy migration were found to be consistent with the set and reset pulse voltage obtained from experiments. Understanding this mechanism will be beneficial to effectively realizing the materials design in these devices.     

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.     

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.     

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.     

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.     

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.     

Performance analysis of 20 nm gate-length In0.2Al0.8N/GaN HEMT with Cu-gate having a remarkable high ION/IOFF ratio

Abstract： We propose a new structure of InxAll-xN/GaN high electron mobility transistor （HEMT） with gate length of 20 nm. The threshold voltage of this HEMT is achieved as -0.472 V. In this device the InA1N barrier layer is intentionally n-doped to boost the ION/IOFF ratio. The InAlN layer acts as donor barrier layer for this HEMT which exhibits an ION = 10-4.3 A and a very low IOFF = 10-14.4 A resulting in an ION/IoFF ratio of 1010.1. We compared our obtained results with the conventional InAlN/GaN HEMT device having undoped barrier and found that the proposed device has almost l0s times better ION/IOFF ratio. Further, the mobility analysis in GaN channel of this proposed HEMT structure along with DC analysis, C-V and conductance characteristics by using small-signal analysis are also presented in this paper. Moreover, the shifts in threshold voltage by DIBL effect and gate leakage current in the proposed HEMT are also discussed. InAlN was chosen as the most preferred barrier layer as a replacement of AlGaN for its excellent thermal conductivity and very good scalability.     

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.     

All‐Polymer Bistable Resistive Memory Device Based on Nanoscale Phase‐Separated PCBM‐Ferroelectric Blends

All polymer nonvolatile bistable memory devices are fabricated from blends of ferroelectric poly(vinylidenefluoride–trifluoroethylene (P(VDF‐TrFE)) and n‐type semiconducting [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM). The nanoscale phase separated films consist of PCBM domains that extend from bottom to top electrode, surrounded by a ferroelectric P(VDF‐TrFE) matrix. Highly conducting poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) polymer electrodes are used to engineer band offsets at the interfaces. The devices display resistive switching behavior due to modulation of this injection barrier. With careful optimization of the solvent and processing conditions, it is possible to spin cast very smooth blend films (R_rms ≈ 7.94 nm) and with good reproducibility. The devices exhibit high I_on/I_off ratios (≈3 × 10³), low read voltages (≈5 V), excellent dielectric response at high frequencies (?_r ≈ 8.3 at 1 MHz), and excellent retention characteristics up to 10 000 s.     

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.     

High‐Mobility ZnO Thin Film Transistors Based on Solution‐processed Hafnium Oxide Gate Dielectrics

The properties of metal oxides with high dielectric constant (k) are being extensively studied for use as gate dielectric alternatives to silicon dioxide (SiO₂). Despite their attractive properties, these high‐k dielectrics are usually manufactured using costly vacuum‐based techniques. In that respect, recent research has been focused on the development of alternative deposition methods based on solution‐processable metal oxides. Here, the application of the spray pyrolysis (SP) technique for processing high‐quality hafnium oxide (HfO₂) gate dielectrics and their implementation in thin film transistors employing spray‐coated zinc oxide (ZnO) semiconducting channels are reported. The films are studied by means of admittance spectroscopy, atomic force microscopy, X‐ray diffraction, UV–Visible absorption spectroscopy, FTIR, spectroscopic ellipsometry, and field‐effect measurements. Analyses reveal polycrystalline HfO₂ layers of monoclinic structure that exhibit wide band gap (≈5.7 eV), low roughness (≈0.8 nm), high dielectric constant (k ≈ 18.8), and high breakdown voltage (≈2.7 MV/cm). Thin film transistors based on HfO₂/ZnO stacks exhibit excellent electron transport characteristics with low operating voltages (≈6 V), high on/off current modulation ratio (～10⁷) and electron mobility in excess of 40 cm² V^?1 s^?1.     

Organic memristive devices based on silver nanoparticles and DNA

A novel organic memory device ‘Al/silver nanoparticles-deoxyribonucleic acid-cetyltrimethylammonium Bromide/ITO’ (Al/Ag NPs–DNA–CTMA/ITO) was fabricated. The measured I–V curve of the device exhibits unipolar switching. The conductivity and the memristive characteristics are significantly improved by the introduction of Ag nanoparticles, but with a poor stability. Better stability is achieved by annealing the device, which also changes the switching characteristic from unipolar to bipolar. As the annealing temperature is raised, the switching voltage first decreases and then increases, while the current I_RESET first increases and then decreases. The range of the optimal annealing temperature is from 383 K to 403 K and the maximum ON/OFF current ratio (I_ON/I_OFF) can reach 10⁴. The switching voltage, the current, and I_ON/I_OFF all increase with the applied voltage amplitude, and V_SET and I_ON/I_OFF obey a quadratic and Boltzmann relationship, respectively.     

Ferroelectricity-modulated resistive switching in Pt/Si:HfO2/HfO2-x/Pt memory

It is investigated for the effect of a ferroelectric Si:HfO₂ thin film on the resistive switching in a stacked Pt/Si:HfO₂/highly-oxygen-deficient HfO_2-x/Pt structure. Improved resistance performance was observed. It was concluded that the observed resistive switching behavior was related to the modulation of the width and height of a depletion barrier in the HfO_2-x layer, which was caused by the Si:HfO₂ ferroelectric polarization field effect. Reliable switching reproducibility and long data retention were observed in these memory cells, suggesting their great potential in non-volatile memories applications with full compatibility and simplicity.     

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.     

Fully Transparent p‐MoTe2 2D Transistors Using Ultrathin MoOx/Pt Contact Media for Indium‐Tin‐Oxide Source/Drain

Since transition metal dichalcogenide (TMD) semiconductors are found as 2D van der Waals materials with a discrete energy bandgap, many 2D‐like thin field effect transistors (FETs) and PN diodes are reported as prototype electrical and optoelectronic devices. As a potential application of display electronics, transparent 2D FET devices are also reported recently. Such transparent 2D FETs are very few in report, yet no p‐type channel 2D‐like FETs are seen. Here, 2D‐like thin transparent p‐channel MoTe₂ FETs with oxygen (O₂) plasma‐induced MoO_x/Pt/indium‐tin‐oxide (ITO) contact are reported for the first time. For source/drain contact, 60 s short O₂ plasma and ultrathin Pt‐deposition processes on MoTe₂ surface are sequentially introduced before ITO thin film deposition and patterning. As a result, almost transparent 2D FETs are obtained with a decent mobility of ≈5 cm² V^?1 s^?1, a high ON/OFF current ratio of ≈10⁵, and 70% transmittance. In particular, for normal MoTe₂ FETs without ITO, O₂ plasma process greatly improves the hole injection efficiency and device mobility (≈60 cm² V^?1 s^?1), introducing ultrathin MoO_x between Pt source/drain and MoTe₂. As a final device application, a photovoltaic current modulator, where the transparent FET stably operates as gated by photovoltaic effects, is integrated.     

Low-Energy Oxygen Plasma Injection of 2D Bi2Se3 Realizes Highly Controllable Resistive Random Access Memory

Resistive random access memory (RRAM) based on ultrathin 2D materials is considered to be a very feasible solution for future data storage and neuromorphic computing technologies. However, controllability and stability are the problems that need to be solved for practical applications. Here, by introducing a damage-less ion implantation technology using ultralow-energy plasma, the transport mechanisms of space charge limited current and Schottky emission are successfully realized and controlled in RRAM based on 2D Bi₂Se₃ nanosheets. The memristors exhibit stable resistive switching behavior with a high resistive switching ratio (>10⁴), excellent cycling endurances (300 cycles), and great retention performance (>10⁴ s). The reliability and controllability of Bi₂Se₃ memory endowed by oxygen plasma injection demonstrate the great potential of this ultralow-energy ion implantation technology in the application of 2D RRAM.     

Zr‐Doped Indium Oxide (IZRO) Transparent Electrodes for Perovskite‐Based Tandem Solar Cells

Parasitic absorption in transparent electrodes is one of the main roadblocks to enabling power conversion efficiencies (PCEs) for perovskite‐based tandem solar cells beyond 30%. To reduce such losses and maximize light coupling, the broadband transparency of such electrodes should be improved, especially at the front of the device. Here, the excellent properties of Zr‐doped indium oxide (IZRO) transparent electrodes for such applications, with improved near‐infrared (NIR) response, compared to conventional tin‐doped indium oxide (ITO) electrodes, are shown. Optimized IZRO films feature a very high electron mobility (up to ≈77 cm² V^?1 s^?1), enabling highly infrared transparent films with a very low sheet resistance (≈18 Ω □^?1 for annealed 100 nm films). For devices, this translates in a parasitic absorption of only ≈5% for IZRO within the solar spectrum (250–2500 nm range), to be compared with ≈10% for commercial ITO. Fundamentally, it is found that the high conductivity of annealed IZRO films is directly linked to promoted crystallinity of the indium oxide (In₂O₃) films due to Zr‐doping. Overall, on a four‐terminal perovskite/silicon tandem device level, an absolute 3.5 mA cm^?2 short‐circuit current improvement in silicon bottom cells is obtained by replacing commercial ITO electrodes with IZRO, resulting in improving the PCE from 23.3% to 26.2%.     

Performance‐Enhancing Selector via Symmetrical Multilayer Design

Two‐terminal selectors with high nonlinearity, based on bidirectional threshold switching (TS) behaviors, are considered as a crucial element of crossbar integration for emerging nonvolatile memory and neuromorphic network. Although great efforts have been made to obtain various selectors, existing selectors cannot fully satisfy the rigorous standard of assorted memristive elements and it is in great demand to enhance the performance. Here, a new type of Ag/TaO_x/TaO_y/TaO_x/Ag (x < y) selector based on homogeneous trilayered oxides is developed to attain the required parameters including bidirectional TS operation, a large selectivity of ≈10¹⁰, a high compliance current up to 1 mA, and ultralow switching voltages under 0.2 V. Tunable operation voltages can be realized by modulating the thickness of inserted TaO_y. All‐TaO_x‐based integrated 1S1R (one selector and one memristor) cells, prepared completely by magnetron sputtering and no need of a middle electrode, exhibit a nonlinear feature, which is quite characteristic for the crossbar devices, avoiding undesired crosstalk current issues. The tantalum‐oxide‐based homojunctions offer high insulation, low ion mobility, and rich interfaces, which is responsible for the modulation of Ag conductive filaments and corresponding high‐performance cation‐based selector. These findings might advance practical implementation of two‐terminal selectors in emerging memories, especially resistive random access memories.     

Improving retention properties by thermal imidization for polyimide-based nonvolatile resistive random access memories

In this study, a polyimide (PI) thin film was synthesized as a resistive layer for creating resistive random access memory (ReRAM). The switch between high- and low-resistance states is caused by the formation and dissociation of dipole direction and Schottky barrier. The impact of imidization on memory properties was evaluated in detail by clarifying the transmission mechanism, and reliability properties including retention and endurance were improved using thermal imidization. In addition, the proposed PI-based ReRAM demonstrated superior performance levels compared with those of electrochemical-metallization-based and valence-change-based ReRAMs, including higher R_ON/R_OFF ratio (> 10⁷) and lower operation energy (< 0.16 MV/cm).