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.     

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.     

Highly Uniform,Electroforming‐Free,and Self‐Rectifying Resistive Memory in the Pt/Ta2O5/HfO2‐x/TiN Structure

The development of a resistance switching (RS) memory cell that contains rectification functionality in itself, highly reproducible RS performance, and electroforming‐free characteristics is an impending task for the development of resistance switching random access memory. In this work, a two‐layered dielectric structure consisting of HfO₂ and Ta₂O₅ layers, which are in contact with the TiN and Pt electrode, is presented for achieving these tasks simultaneously in one sample configuration. The HfO₂ layer works as the resistance switching layer by trapping or detrapping of electronic carriers, whereas the Ta₂O₅ layer remains intact during the whole switching cycle, which provides the rectification. With the optimized structure and operation conditions for the given materials, excellent RS uniformity, electroforming‐free, and self‐rectifying functionality could be simultaneously achieved from the Pt/Ta₂O₅/HfO₂/TiN structure.     

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.     

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.     

Enhanced Interfacial Stability of Hybrid‐Electrolyte Lithium‐Sulfur Batteries with a Layer of Multifunctional Polymer with Intrinsic Nanoporosity

The use of lithium‐ion conductive solid electrolytes offers a promising approach to address the polysulfide shuttle and the lithium‐dendrite problems in lithium‐sulfur (Li‐S) batteries. One critical issue with the development of solid‐electrolyte Li‐S batteries is the electrode–electrolyte interfaces. Herein, a strategic approach is presented by employing a thin layer of a polymer with intrinsic nanoporosity (PIN) on a Li⁺‐ion conductive solid electrolyte, which significantly enhances the ionic interfaces between the electrodes and the solid electrolyte. Among the various types of Li⁺‐ion solid electrolytes, NASICON‐type Li_1+xAl_xTi_2‐x(PO₄)₃ (LATP) offers advantages in terms of Li⁺‐ion conductivity, stability in ambient environment, and practical viability. However, LATP is susceptible to reaction with both the Li‐metal anode and polysulfides in Li‐S batteries due to the presence of easily reducible Ti⁴⁺ ions in it. The coating with a thin layer of PIN presented in this study overcomes the above issues. At the negative‐electrode side, the PIN layer prevents the direct contact of Li‐metal with the LATP solid electrolyte, circumventing the reduction of LATP by Li metal. At the positive electrode side, the PIN layer prevents the migration of polysulfides to the surface of LATP, preventing the reduction of LATP by polysulfides.     

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.     

Influence of the metal electrode on the characteristics of thermal Ta2O5 capacitors

The effect of various electrodes (Al, W, TiN) deposited by evaporation (Al) and sputtering (W, TiN) on the electrical characteristics of thermal thin film (15-35 nm) Ta₂O₅ capacitors has been investigated. The absolute level of leakage currents, breakdown fields, mechanism of conductivity, dielectric constant values are discussed in the terms of possible reactions between Ta₂O₅ and electrode material as well as electrode deposition process-induced defects acting as electrically active centers. The dielectric constant values are in the range 12-26 in dependence on both Ta₂O₅ thickness and gate material. The results show that during deposition of TiN and Al a reaction that worsens the properties of Ta₂O₅ occurs while there is not an indication for detectable reduction of Ta₂O₅ when top electrode is W, and the leakage current is 5-7 orders of magnitude lower as compared to Al and TiN-electroded capacitors. The high level of leakage current for TiN and Al gate capacitors are related to the radiation defects generated in Ta₂O₅ during sputtering of TiN, and damaged interface at the electrode due to a reaction between Al and Ta₂O₅, respectively. It is demonstrated that the quality of the top electrode affects the electrical characteristics of the capacitors and the sputtered W is found to be the best. The sputtered W gate provides Ta₂O₅ capacitors with a good quality: the current density <7 × 10⁻¹⁰ A/cm² at 1 V (0.7 MV/cm, 15 nm thick Ta₂O₅). W deposition is not accompanied by an introduction of a detectable damage leading to a change of the properties of the initial as-grown Ta₂O₅ as in the case of TiN electrode. Damage introduced during TiN sputtering is responsible for current deterioration (high leakage current) and poor breakdown characteristics. It is concluded that the sputtered W top electrode is a good candidate as a top electrode of storage capacitors in dynamic random access memories giving a stable contact with Ta₂O₅, but sputtering technique is less suitable (favorable) for deposition of TiN as a metal electrode due to the introduction of radiation defects causing both deterioration of leakage current and poor breakdown characteristics.     

Effect of the top electrode material on the resistive switching of TiO2 thin film

Effect of the top electrode (TE) metal on the resistive switching of (TE)/TiO₂/Pt structure was investigated. It was confirmed that the potential barrier height between the metal and TiO₂ is an important factor on the resistive switching characteristics. When high Schottky barrier was formed with the TiO₂ film, using Pt or Au as a top electrode, both stable URS (unipolar) and BRS (bipolar resistive switching) characteristics were observed depending on the current compliance level. In the case of Ag, which forms a relatively low Schottky barrier, only BRS characteristics were observed, regardless of the current compliance level. In the case of Ni and Al, which have similar work function as Ag, unstable URS and BRS at very low current compliance levels were observed due to a chemical reaction at the interface. For the Ti electrode, resistive switching was not observed, because the work function of Ti is lower than that of TiO₂ and TiO phase was formed at the interface (Ti/TiO_x contact is ohmic).     

Fabrication of a Cu‐Cone‐Shaped Cation Source Inserted Conductive Bridge Random Access Memory and Its Improved Switching Reliability

Conductive bridge random access memory (CBRAM) has been regarded as a promising candidate for the next‐generation nonvolatile memory technology. Even with the great performance of CBRAM, the global generation and overinjection of cations after much repetitive switching cannot be prevented. The overinjection of cations into an electrolyte layer causes high‐resistance‐state resistance (R_HRS) degradation, on/off ratio reduction, and eventual switching failure. It also degrades the switching uniformity. In this work, a Cu‐cone‐structure‐embedded TiN/TiO₂/Cu cone/TiN device is fabricated to alleviate the problems of Cu‐based CBRAM, mentioned above. The fabrication method of the device, which is useful for laboratory scale experiment, is developed, and its superior switching performance and reliability compared with the conventional planar device. The insertion of the Cu cone structure allows the placement of only a limited amount of cation source in each cell, and the embedded conical structure also concentrates the applied electric field, which enables filament growth control. Furthermore, the concentrated field localizes the resistive switching on the tip area of the cone structure, which makes the effective switching area about tens of nanometers even for the much larger area of the entire electrode (several µm²).     

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.     

Self‐Limited Switching in Ta2O5/TaOx Memristors Exhibiting Uniform Multilevel Changes in Resistance

To facilitate the development of memristive devices, it is essential to resolve the problem of non‐uniformity in switching, which is caused by the random nature of the filamentary switching mechanism in many resistance switching memories based on transition metal oxide. In addition, device parameters such as low‐ and high‐state resistance should be regulated as desired. These issues can be overcome if memristive devices have switching limits for both the low‐ and high‐resistance states and if their resistance values are highly controllable. In this study, a method termed self‐limited switching for uniformly regulating the values of both the low‐ and high‐resistance states is suggested, and the circuit configuration required for the self‐limited switching is established in a Ta₂O₅/TaO_x memristive structure. A method of improving the uniformity of multi‐level resistance states in this memristive system is also proposed.     

Resistive switching characteristics of ultra-thin TiOx

We investigated the resistive switching characteristics of Ir/TiO_x/TiN structure with 50 nm active area. We successfully formed ultra-thin (4 nm) TiO_x active layer using oxidation process of TiN BE, which was confirmed by X-ray Photoelectron Spectroscopy (XPS) depth profiling. Compared to large area device (50 μm), which shows only ohmic behavior, 250 and 50 nm devices show very stable resistive switching characteristics. Due to the formation and rupture of oxygen vacancies induced conductive filament at Ir and TiO_x interface, bipolar resistive switching was occurred. We obtained excellent switching endurance up to 10⁶ times with 100 ns pulse and negligible degradation of each resistance state at 85 °C up to 10⁴ s.     

Facile Synthesis of Blocky SiOx/C with Graphite‐Like Structure for High‐Performance Lithium‐Ion Battery Anodes

SiO_x‐containing graphite composites have aroused great interests as the most promising alternatives for practical application in high‐performance lithium‐ion batteries. However, limited loading amount of SiO_x on the surface of graphite and some inherent disadvantages of SiO_x such as huge volume variation and poor electronic conductivity result in unsatisfactory electrochemical performance. Herein, a novel and facile fabrication approach is developed to synthesize high‐performance SiO_x/C composites with graphite‐like structure in which SiO_x particles are dispersed and anchored in the carbon materials by restoring original structure of artificial graphite. The multicomponent carbon materials are favorable for addressing the disadvantages of SiO_x‐based anodes, especially for the formation of stable solid electrolyte interphase, maintaining structural integrity of electrode materials and improving electrical conductivity of electrode. The resultant SiO_x/C anodes demonstrate high reversible capacities (645 mA h g^?1), excellent cycling stability (≈90% capacity retention for 500 cycles), and superior rate capabilities. Even at high pressing density (1.3 g cm^?3), SiO_x/C anodes still present superior cycling performance due to the high tap density and structural integrity of electrode materials. The proposed synthetic method can also be developed to address other anode materials with inferior electronic conductivity and huge volume variation.     

MXene‐Bonded Flexible Hard Carbon Film as Anode for Stable Na/K‐Ion Storage

Hard carbon (HC) is a promising anode material for sodium‐ion batteries (SIBs) and potassium‐ion batteries (PIBs), but the volume change during the insertion/extraction of Na⁺ or K⁺ limits the cycle life, especially for PIBs due to the large ion size of K⁺. Moreover, the conventional anodes fabricated through the coating method cannot satisfy the requirement of flexible devices. Here, it is shown that 2D carbide flakes of Ti₃C₂T_x MXene can be used as multifunctional conductive binders for flexible HC electrodes. The use of MXene nanosheets eliminates the need for all the electrochemically inactive components in the conventional polyvinylidene fluoride–bonded HC electrode, including polymer binders, conductive additives, and current collectors. In MXene‐bonded HC electrodes, conductive and hydrophilic MXene 2D nanosheets construct a 3D network, which can effectively stabilize the electrode structure and accommodate the volume expansion of HC during the charge/discharge process, leading to an enhanced electrode capacity and excellent cycle performance as anodes for both SIBs and PIBs. Benefiting from the 3D conductive network, the MXene‐bonded HC film electrodes also present improved rate capability, indicating MXene is a very promising multifunctional binder for next‐generation flexible secondary rechargeable batteries.     

Micrometer‐Sized RuO2 Catalysts Contributing to Formation of Amorphous Na‐Deficient Sodium Peroxide in Na–O2 Batteries

The results obtained herein demonstrate that the oxygen electrode plays a critical role in determining the morphology and chemical composition of discharge products in Na–O₂ batteries. Micrometer‐sized cubic NaO₂, film‐like NaO₂, and nano‐sized amorphous spherical Na_2‐xO₂ are characterized as the main discharge products on the surface of reduced graphite oxide (rGO), boron‐doped rGO (B‐rGO), and micrometer‐sized RuO₂ catalyst‐coated B‐rGO (m‐RuO₂‐B‐rGO) cathodes, respectively. The Na–O₂ battery with m‐RuO₂‐B‐rGO as the cathode exhibits a much longer cycle life than those with the other cathodes, maintaining an unchanged capacity (0.5 mAh cm^‐2) after 100 cycles at a current density of 0.05 mA cm^‐2. A good rate capability and deep discharge–charge energy efficiency are also obtained. The excellent electrochemical performance of the battery is attributed to the effect of the micrometer‐sized RuO₂ catalyst. Owing to the high affinity of RuO₂ for oxygen, the amorphous phase Na_2‐xO₂ discharge product, which has good electrical contact with the RuO₂ particles, can decompose completely under 3.1 V without a sudden voltage jump. Meanwhile, the micrometer‐sized RuO₂ catalysts also provide enough active sites and space for the reactions, and effectively minimize the occurrence of side reactions between discharge products and carbon defects.     

Autogenous Growth of Hierarchical NiFe(OH)x/FeS Nanosheet‐On‐Microsheet Arrays for Synergistically Enhanced High‐Output Water Oxidation

Practical electrochemical water splitting requires cost‐effective electrodes capable of steadily working at high output, leading to the challenges for efficient and stable electrodes for the oxygen evolution reaction (OER). Herein, by simply using conductive FeS microsheet arrays vertically pre‐grown on iron foam (FeS/IF) as both substrate and source to in situ form vertically aligned NiFe(OH)_x nanosheets arrays, a hierarchical electrode with a nano/micro sheet‐on‐sheet structure (NiFe(OH)_x/FeS/IF) can be readily achieved to meet the requirements. Such hierarchical electrode architecture with a superhydrophilic surface also allows for prompt gas release even at high output. As a result, NiFe(OH)_x/FeS/IF exhibits superior OER activity with an overpotential of 245 mV at 50 mA cm^?2 and can steadily output 1000 mA cm^?2 at a low overpotential of 332 mV. The water‐alkali electrolyzer using NiFe(OH)_x/FeS/IF as the anode can deliver 10 mA cm^?2 at 1.50 V and steadily operate at 300 mA cm^?2 with a small cell voltage for 70 h. Furthermore, a solar‐driven electrolyzer using the developed electrode demonstrates an exceptionally high solar‐to‐hydrogen efficiency of 18.6%. Such performance together with low‐cost Fe‐based materials and facile mass production suggest the present strategy may open up opportunities for rationally designing hierarchical electrocatalysts for practical water splitting or diverse applications.     

VOx@MoO3 Nanorod Composite for High‐Performance Supercapacitors

Vanadium oxide is a promising pseudocapacitive electrode, but their capacitance, especially at high current densities, requires improvement for practical applications. Herein, a VO_x@MoO₃ composite electrode is constructed through a facile electrochemical method. Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy demonstrate a modification on the chemical environment and electronic structure of VO_x upon the effective interaction with the thin layer of MoO₃. A careful investigation of the electrochemical impedance spectroscopy data reveals much enhanced power capability of the composite electrode. More charge storage sites will also be created at/near the heterogeneous interface. Due to those synergistic effects, the VO_x@MoO₃ electrode shows excellent electrochemical performance. It provides a high capacitance of 1980 mF cm⁻² at 2 mA cm⁻². Even at the high current density of 100 mA cm⁻², it still achieves 1166 mF cm⁻² capacitance, which doubles the sum of single electrodes. The MoO₃ layer also helps to prevent VO_x structure deformation, and 94% capacitance retention over 10 000 cycles is obtained for the composite electrode. This work demonstrates an effective strategy to induce interactions between heterogeneous components and enhance the electrochemical performance, which can also be applied to other pseudocapacitive electrode candidates.     

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.     

Oxygen‐Deficient Homo‐Interface toward Exciting Boost of Pseudocapacitance

Pseudocapacitors hold great promise as charge storage systems that combine battery‐level energy density and capacitor‐level power density. The utilization of pseudocapacitive material, however, is usually restricted to the surface due to poor electrode kinetics, leading to less accessible charge storage sites and limited capacitance. Here, tin oxide is successfully endowed with outstanding pseudocapacitance and fast electrode kinetics in a negative potential window by engineering oxygen‐deficient homo‐interfaces. The as‐prepared SnO_2?x@SnO_2?x electrode yields a specific capacitance of 376.6 F g^?1 at the current density of 2.5 A g^?1 and retains 327 F g^?1 at a high current density of 80 A g^?1. The theoretical calculation reveals that the oxygen defects are more favorable at homo‐interfaces than at the surface due to the lower defect formation energy. Meanwhile, as compared with the surface, the homo‐interface possesses more stable Li⁺ storage sites that are readily accessed by Li⁺ due to the occurrence of oxygen vacancies, enabling outstanding pseudocapacitance as well as high rate capability. This oxygen‐deficient homo‐interface design opens up new opportunities to develop high‐energy and power pseudocapacitors.