Wafer-Scalable Single-Layer Amorphous Molybdenum Trioxide.

Molybdenum trioxide (MoO3), an important transition metal oxide (TMO), has been extensively investigated over the past few decades due to its potential in existing and emerging technologies, including catalysis, energy and data storage, electrochromic devices, and sensors. Recently, the growing interest in two-dimensional (2D) materials, often rich in interesting properties and functionalities compared to their bulk counterparts, has led to the investigation of 2D MoO3. However, the realization of large-area true 2D (single to few atom layers thick) MoO3 is yet to be achieved. Here, we demonstrate a facile route to obtain wafer-scale monolayer amorphous MoO3 using 2D MoS2 as a starting material, followed by UV-ozone oxidation at a substrate temperature as low as 120 °C. This simple yet effective process yields smooth, continuous, uniform, and stable monolayer oxide with wafer-scale homogeneity, as confirmed by several characterization techniques, including atomic force microscopy, numerous spectroscopy methods, and scanning transmission electron microscopy. Furthermore, using the subnanometer MoO3 as the active layer sandwiched between two metal electrodes, we demonstrate the thinnest oxide-based nonvolatile resistive switching memory with a low voltage operation and a high ON/OFF ratio. These results (potentially extendable to other TMOs) will enable further exploration of subnanometer stoichiometric MoO3, extending the frontiers of ultrathin flexible oxide materials and devices.

A Library of Atomically Thin 2D Materials Featuring the Conductive-Point Resistive Switching Phenomenon.

Non-volatile resistive switching (NVRS) is a widely available effect in transitional metal oxides, colloquially known as memristors, and of broad interest for memory technology and neuromorphic computing. Until recently, NVRS was not known in other transitional metal dichalcogenides (TMDs), an important material class owing to their atomic thinness enabling the ultimate dimensional scaling. Here, various monolayer or few-layer 2D materials are presented in the conventional vertical structure that exhibit NVRS, including TMDs (MX2 , M = transitional metal, e.g., Mo, W, Re, Sn, or Pt; X = chalcogen, e.g., S, Se, or Te), TMD heterostructure (WS2 /MoS2 ), and an atomically thin insulator (h-BN). These results indicate the universality of the phenomenon in 2D non-conductive materials, and feature low switching voltage, large ON/OFF ratio, and forming-free characteristic. A dissociation-diffusion-adsorption model is proposed, attributing the enhanced conductance to metal atoms/ions adsorption into intrinsic vacancies, a conductive-point mechanism supported by first-principle calculations and scanning tunneling microscopy characterizations. The results motivate further research in the understanding and applications of defects in 2D materials.

Observation of single-defect memristor in an MoS2 atomic sheet.

Non-volatile resistive switching, also known as memristor1 effect, where an electric field switches the resistance states of a two-terminal device, has emerged as an important concept in the development of high-density information storage, computing and reconfigurable systems2-9. The past decade has witnessed substantial advances in non-volatile resistive switching materials such as metal oxides and solid electrolytes. It was long believed that leakage currents would prevent the observation of this phenomenon for nanometre-thin insulating layers. However, the recent discovery of non-volatile resistive switching in two-dimensional monolayers of transition metal dichalcogenide10,11 and hexagonal boron nitride12 sandwich structures (also known as atomristors) has refuted this belief and added a new materials dimension owing to the benefits of size scaling10,13. Here we elucidate the origin of the switching mechanism in atomic sheets using monolayer MoS2 as a model system. Atomistic imaging and spectroscopy reveal that metal substitution into a sulfur vacancy results in a non-volatile change in the resistance, which is corroborated by computational studies of defect structures and electronic states. These findings provide an atomistic understanding of non-volatile switching and open a new direction in precision defect engineering, down to a single defect, towards achieving the smallest memristor for applications in ultra-dense memory, neuromorphic computing and radio-frequency communication systems2,3,11.

Understanding of multiple resistance states by current sweeping in MoS2-based non-volatile memory devices.

Recently, various two-dimensional materials have been reported to exhibit non-volatile resistance switching phenomenon. The atomristors, featuring memristor effect in atomically thin nanomaterials such as monolayer transition metal dichalcogenides and hexagonal boron nitride, have drawn much attention due to the extremely thin active layer thickness with the advantages of forming-free characteristic, large on/off resistance ratio and fast switching speed. To investigate the switching mechanisms in the 2D monolayers, we introduced an electrical characterization method by current sweeping to illustrate the detailed information hidden in the commonly used voltage-sweep curves. Multiple transition steps have been observed in the SET process of MoS2-based resistance switching devices. The different behaviors of transition steps were attributed to the number of defects or vacancies associated with the switching phenomenon, which is consistent with the previously reported conductive-bridge-like model for 2D atomristors. This work provides an approach using current sweeping to precisely characterize the resistance switching effect and inspires further research to optimize the defect distribution in 2D materials for the applications in multi-bit non-volatile memory and neuromorphic computing.

Resistance state evolution under constant electric stress on a MoS2 non-volatile resistive switching device.

MoS2 has been reported to exhibit a resistive switching phenomenon in a vertical metal-insulator-metal (MIM) structure and has attracted much attention due to its ultra-thin active layer thickness. Here, the resistance evolutions in the high resistance state (HRS) and low resistance state (LRS) are investigated under constant voltage stress (CVS) or constant current stress (CCS) on MoS2 resistive switching devices. Interestingly, compared with bulk transition metal oxides (TMO), MoS2 exhibits an opposite characteristic in the fresh or pre-RESET device in the "HRS" wherein the resistance will increase to an even higher resistance after applying CVS, a unique phenomenon only accessible in 2D-based resistive switching devices. It is inferred that instead of in the highest resistance state, the fresh or pre-RESET devices are in an intermediate state with a small amount of Au embedded in the MoS2 film. Inspired by the capability of both bipolar and unipolar operation, positive and negative CVS measurements are performed and show similar characteristics. In addition, it is observed that the resistance state transition is faster when using higher electric stress. Numerical simulations have been performed to study the temperature effect with small-area integration capability. These results can be explained by a modified conductive-bridge-like model based on Au migration, uncovering the switching mechanisms in the ultrathin 2D materials and inspiring future studies in this area.

Thinnest Nonvolatile Memory Based on Monolayer h-BN.

2D materials have attracted much interest over the past decade in nanoelectronics. However, it was believed that the atomically thin layered materials are not able to show memristive effect in vertically stacked structure, until the recent discovery of monolayer transition metal dichalcogenide (TMD) atomristors, overcoming the scaling limit to sub-nanometer. Herein, the nonvolatile resistance switching (NVRS) phenomenon in monolayer hexagonal boron nitride (h-BN), a typical 2D insulator, is reported. The h-BN atomristors are studied using different electrodes and structures, featuring forming-free switching in both unipolar and bipolar operations, with large on/off ratio (up to 107 ). Moreover, fast switching speed (<15 ns) is demonstrated via pulse operation. Compared with monolayer TMDs, the one-atom-thin h-BN sheet reduces the vertical scaling to ≈0.33 nm, representing a record thickness for memory materials. Simulation results based on ab-initio method reveal that substitution of metal ions into h-BN vacancies during electrical switching is a likely mechanism. The existence of NVRS in monolayer h-BN indicates fruitful interactions between defects, metal ions and interfaces, and can advance emerging applications on ultrathin flexible memory, printed electronics, neuromorphic computing, and radio frequency switches.

Zero-static power radio-frequency switches based on MoS2 atomristors.

Recently, non-volatile resistance switching or memristor (equivalently, atomristor in atomic layers) effect was discovered in transitional metal dichalcogenides (TMD) vertical devices. Owing to the monolayer-thin transport and high crystalline quality, ON-state resistances below 10 Ω are achievable, making MoS2 atomristors suitable as energy-efficient radio-frequency (RF) switches. MoS2 RF switches afford zero-hold voltage, hence, zero-static power dissipation, overcoming the limitation of transistor and mechanical switches. Furthermore, MoS2 switches are fully electronic and can be integrated on arbitrary substrates unlike phase-change RF switches. High-frequency results reveal that a key figure of merit, the cutoff frequency (fc), is about 10 THz for sub-µm2 switches with favorable scaling that can afford fc above 100 THz for nanoscale devices, exceeding the performance of contemporary switches that suffer from an area-invariant scaling. These results indicate a new electronic application of TMDs as non-volatile switches for communication platforms, including mobile systems, low-power internet-of-things, and THz beam steering.

Atomristor: Nonvolatile Resistance Switching in Atomic Sheets of Transition Metal Dichalcogenides.

Recently, two-dimensional (2D) atomic sheets have inspired new ideas in nanoscience including topologically protected charge transport,1,2 spatially separated excitons,3 and strongly anisotropic heat transport.4 Here, we report the intriguing observation of stable nonvolatile resistance switching (NVRS) in single-layer atomic sheets sandwiched between metal electrodes. NVRS is observed in the prototypical semiconducting (MX2, M = Mo, W; and X = S, Se) transitional metal dichalcogenides (TMDs),5 which alludes to the universality of this phenomenon in TMD monolayers and offers forming-free switching. This observation of NVRS phenomenon, widely attributed to ionic diffusion, filament, and interfacial redox in bulk oxides and electrolytes,6-9 inspires new studies on defects, ion transport, and energetics at the sharp interfaces between atomically thin sheets and conducting electrodes. Our findings overturn the contemporary thinking that nonvolatile switching is not scalable to subnanometre owing to leakage currents.10 Emerging device concepts in nonvolatile flexible memory fabrics, and brain-inspired (neuromorphic) computing could benefit substantially from the wide 2D materials design space. A new major application, zero-static power radio frequency (RF) switching, is demonstrated with a monolayer switch operating to 50 GHz.

Electrodeposition of porous graphene networks on nickel foams as supercapacitor electrodes with high capacitance and remarkable cyclic stability.

We describe a facile, low-cost, and green method to fabricate porous graphene networks/nickel foam (PG/NF) electrodes by electrochemical deposition of graphene sheets on nickel foams (NFs) for the application of supercapacitor electrodes. The electrodeposition process was accomplished by electrochemical reduction of graphene oxide (GO) in its aqueous suspension. The resultant binder-free PG/NF electrodes exhibited excellent double-layer capacitive performance with a high rate capability and a high specific capacitance of 183.2 mF cm(-2) at the current density of 1 mA cm(-2). Moreover, the specific capacitance maintains nearly 100% over 10,000 charge-discharge cycles, demonstrating a remarkable cyclic stability of these porous supercapacitor electrodes. PACS: 82.47.Uv (Electrochemical capacitors); 82.45.Fk (Electrodes electrochemistry); 81.05.Rm (Fabrication of porous materials).