Hybrid Flexible Resistive Random Access Memory‐Gated Transistor for Novel Nonvolatile Data Storage

Here, a single‐device demonstration of novel hybrid architecture is reported to achieve programmable transistor nodes which have analogies to flash memory by incorporating a resistive switching random access memory (RRAM) device as a resistive switch gate for field effect transistor (FET) on a flexible substrate. A high performance flexible RRAM with a three‐layered structure is fabricated by utilizing solution‐processed MoS₂ nanosheets sandwiched between poly(methyl methacrylate) polymer layers. Gate coupling with the pentacene‐based transistor can be controlled by the RRAM memory state to produce a nonprogrammed state (inactive) and a programmed state (active) with a well‐defined memory window. Compared to the reference flash memory device based on the MoS₂ floating gate, the hybrid device presents robust access speed and retention ability. Furthermore, the hybrid RRAM‐gated FET is used to build an integrated logic circuit and a wide logic window in inverter logic is achieved. The controllable, well‐defined memory window, long retention time, and fast access speed of this novel hybrid device may open up new possibilities of realizing fully functional nonvolatile memory for high‐performance flexible electronics.     

A High‐On/Off‐Ratio Floating‐Gate Memristor Array on a Flexible Substrate via CVD‐Grown Large‐Area 2D Layer Stacking

Memristors such as phase‐change memory and resistive memory have been proposed to emulate the synaptic activities in neuromorphic systems. However, the low reliability of these types of memories is their biggest challenge for commercialization. Here, a highly reliable memristor array using floating‐gate memory operated by two terminals (source and drain) using van der Waals layered materials is demonstrated. Centimeter‐scale samples (1.5 cm × 1.5 cm) of MoS₂ as a channel and graphene as a trap layer grown by chemical vapor deposition (CVD) are used for array fabrication with Al₂O₃ as the tunneling barrier. With regard to the memory characteristics, 93% of the devices exhibit an on/off ratio of over 10³ with an average ratio of 10⁴. The high on/off ratio and reliable endurance in the devices allow stable 6‐level memory applications. The devices also exhibit excellent memory durability over 8000 cycles with a negligible shift in the threshold voltage and on‐current, which is a significant improvement over other types of memristors. In addition, the devices can be strained up to 1% by fabricating on a flexible substrate. This demonstration opens a practical route for next‐generation electronics with CVD‐grown van der Waals layered materials.     

Structural Phase Transition Effect on Resistive Switching Behavior of MoS2‐Polyvinylpyrrolidone Nanocomposites Films for Flexible Memory Devices

The 2H phase and 1T phase coexisting in the same molybdenum disulfide (MoS₂) nanosheets can influence the electronic properties of the materials. The 1T phase of MoS₂ is introduced into the 2H‐MoS₂ nanosheets by two‐step hydrothermal synthetic methods. Two types of nonvolatile memory effects, namely write‐once read‐many times memory and rewritable memory effect, are observed in the flexible memory devices with the configuration of Al/1T@2H‐MoS₂‐polyvinylpyrrolidone (PVP)/indium tin oxide (ITO)/polyethylene terephthalate (PET) and Al/2H‐MoS₂‐PVP/ITO/PET, respectively. It is observed that structural phase transition in MoS₂ nanosheets plays an important role on the resistive switching behaviors of the MoS₂‐based device. It is hoped that our results can offer a general route for the preparation of various promising nanocomposites based on 2D nanosheets of layered transition metal dichalcogenides for fabricating the high performance and flexible nonvolatile memory devices through regulating the phase structure in the 2D nanosheets.     

Size‐Dependent Nonlinear Optical Properties of Atomically Thin Transition Metal Dichalcogenide Nanosheets

Size‐dependent nonlinear optical properties of modification‐free transition metal dichalcogenide (TMD) nanosheets are reported, including MoS₂, WS₂, and NbSe₂. Firstly, a gradient centrifugation method is demonstrated to separate the TMD nanosheets into different sizes. The successful size separation allows the study of size‐dependent nonlinear optical properties of nanoscale TMD materials for the first time. Z‐scan measurements indicate that the dispersion of MoS₂ and WS₂ nanosheets that are 50–60 nm thick leads to reverse saturable absorption (RSA), which is in contrast to the saturable absorption (SA) seen in the thicker samples. Moreover, the NbSe₂ nanosheets show no size‐dependent effects because of their metallic nature. The mechanism behind the size‐dependent nonlinear optical properties of the semiconductive TMD nanosheets is revealed by transient transmission spectra measurements.     

Contact‐Engineered Electrical Properties of MoS2 Field‐Effect Transistors via Selectively Deposited Thiol‐Molecules

Although 2D molybdenum disulfide (MoS₂) has gained much attention due to its unique electrical and optical properties, the limited electrical contact to 2D semiconductors still impedes the realization of high‐performance 2D MoS₂‐based devices. In this regard, many studies have been conducted to improve the carrier‐injection properties by inserting functional paths, such as graphene or hexagonal boron nitride, between the electrodes and 2D semiconductors. The reported strategies, however, require relatively time‐consuming and low‐yield transfer processes on sub‐micrometer MoS₂ flakes. Here, a simple contact‐engineering method is suggested, introducing chemically adsorbed thiol‐molecules as thin tunneling barriers between the metal electrodes and MoS₂ channels. The selectively deposited thiol‐molecules via the vapor‐deposition process provide additional tunneling paths at the contact regions, improving the carrier‐injection properties with lower activation energies in MoS₂ field‐effect transistors. Additionally, by inserting thiol‐molecules at the only one contact region, asymmetric carrier‐injection is feasible depending on the temperature and gate bias.     

Two‐Terminal Multibit Optical Memory via van der Waals Heterostructure

2D van der Waals (vdWs) heterostructures exhibit intriguing optoelectronic properties in photodetectors, solar cells, and light‐emitting diodes. In addition, these materials have the potential to be further extended to optical memories with promising broadband applications for image sensing, logic gates, and synaptic devices for neuromorphic computing. In particular, high programming voltage, high off‐power consumption, and circuital complexity in integration are primary concerns in the development of three‐terminal optical memory devices. This study describes a multilevel nonvolatile optical memory device with a two‐terminal floating‐gate field‐effect transistor with a MoS₂/hexagonal boron nitride/graphene heterostructure. The device exhibits an extremely low off‐current of ≈10^?14 A and high optical switching on/off current ratio of over ≈10⁶, allowing 18 distinct current levels corresponding to more than four‐bit information storage. Furthermore, it demonstrates an extended endurance of over ≈10⁴ program–erase cycles and a long retention time exceeding 3.6 × 10⁴ s with a low programming voltage of ?10 V. This device paves the way for miniaturization and high‐density integration of future optical memories with vdWs heterostructures.     

Nickel@Nitrogen‐Doped Carbon@MoS2 Nanosheets: An Efficient Electrocatalyst for Hydrogen Evolution Reaction

Developing cheap, abundant, and easily available electrocatalysts to drive the hydrogen evolution reaction (HER) at small overpotentials is an urgent demand of hydrogen production from water splitting. Molybdenum disulfide (MoS₂) based composites have emerged as competitive electrocatalysts for HER in recent years. Herein, nickel@nitrogen‐doped carbon@MoS₂ nanosheets (Ni@NC@MoS₂) hybrid sub‐microspheres are presented as HER catalyst. MoS₂ nanosheets with expanded interlayer spacings are vertically grown on nickel@nitrogen‐doped carbon (Ni@NC) substrate to form Ni@NC@MoS₂ hierarchical sub‐microspheres by a simple hydrothermal process. The formed Ni@NC@MoS₂ composites display excellent electrocatalytic activity for HER with an onset overpotential of 18 mV, a low overpotential of 82 mV at 10 mA cm^?2, a small Tafel slope of 47.5 mV dec^?1, and high durability in 0.5 H₂SO₄ solution. The outstanding HER performance of the Ni@NC@MoS₂ catalyst can be ascribed to the synergistic effect of dense catalytic sites on MoS₂ nanosheets with exposed edges and expanded interlayer spacings, and the rapid electron transfer from Ni@NC substrate to MoS₂ nanosheets. The excellent Ni@NC@MoS₂ electrocatalyst promises potential application in practical hydrogen production, and the strategy reported here can also be extended to grow MoS₂ on other nitrogen‐doped carbon encapsulated metal species for various applications.     

Surface Engineering of MoS2 via Laser‐Induced Exfoliation in Protic Solvents

With excellent performance in the hydrogen evolution reaction (HER), molybdenum disulfide (MoS₂) is considered a promising nonprecious candidate to substitute Pt‐based catalysts. Herein, pulsed laser irradiation in liquid is used to realize one‐step exfoliation of bulk 2H‐MoS₂ to ultrastable few‐layer MoS₂ nanosheets. Such prepared MoS₂ nanosheets are rich in S vacancies and metallic 1T phase, which significantly contribute to the boosted catalytic HER activity. Protic solvents play a pivotal role in the production of S vacancies and 2H‐to‐1T phase transition under laser irradiation. MoS₂ exfoliated in an optimal solvent of formic acid exhibits outstanding HER activity with an overpotential of 180 mV at 10 mA cm^?2 and Tafel slope of 54 mV dec^?1.     

Nonlinear Saturable Absorption of Liquid‐Exfoliated Molybdenum/Tungsten Ditelluride Nanosheets

Molybdenum disulfide (MoS₂) and tungsten disulfide (WS₂), two representative transition metal dichalcogenide materials, have captured tremendous interest for their unique electronic, optical, and chemical properties. Compared with MoS₂ and WS₂, molybdenum ditelluride (MoTe₂) and tungsten ditelluride (WTe₂) possess similar lattice structures while having smaller bandgaps (less than 1 eV), which is particularly interesting for applications in the near‐infrared wavelength regime. Here, few‐layer MoTe₂/WTe₂ nanosheets are fabricated by a liquid exfoliation method using sodium deoxycholate bile salt as surfactant, and the nonlinear optical properties of the nanosheets are investigated. The results demonstrate that MoTe₂/WTe₂ nanosheets exhibit nonlinear saturable absorption property at 1.55 μm. Soliton mode‐locking operations are realized separately in erbium‐doped fiber lasers utilizing two types of MoTe₂/WTe₂‐based saturable absorbers, one of which is prepared by depositing the nanosheets on side polished fibers, while the other is fabricated by mixing the nanosheets with polyvinyl alcohol and then evaporating them on substrates. Numerous applications may benefit from the nonlinear saturable absorption features of MoTe₂/WTe₂ nanosheets, such as visible/near‐infrared pulsed laser, materials processing, optical sensors, and modulators.     

Preparation of MoS2‐Polyvinylpyrrolidone Nanocomposites for Flexible Nonvolatile Rewritable Memory Devices with Reduced Graphene Oxide Electrodes

A facile method for exfoliation and dispersion of molybdenum disulfide (MoS₂) with the aid of polyvinylpyrrolidone (PVP) is proposed. The resultant PVP‐coated MoS₂ nanosheets, i.e., MoS₂‐PVP nanocomposites, are well dispersed in the low‐boiling ethanol solvent, facilitating their thin film preparation and the device fabrication by solution processing technique. As a proof of concept, a flexible memory diode with the configuration of reduced graphene oxide (rGO)/MoS₂‐PVP/Al exhibited a typical bistable electrical switching and nonvolatile rewritable memory effect with the function of flash. These experimental results prove that the electrical transition is due to the charge trapping and detrapping behavior of MoS₂ in the PVP dielectric material. This study paves a way of employing two‐dimensional nanomaterials as both functional materials and conducting electrodes for the future flexible data storage.     

Carrier Transport and Photoresponse in GeSe/MoS2 Heterojunction p–n Diodes

Simple stacking of thin van der Waals 2D materials with different physical properties enables one to create heterojunctions (HJs) with novel functionalities and new potential applications. Here, a 2D material p–n HJ of GeSe/MoS₂ is fabricated and its vertical and horizontal carrier transport and photoresponse properties are studied. Substantial rectification with a very high contrast (>10⁴) through the potential barrier in the vertical‐direction tunneling of HJs is observed. The negative differential transconductance with high peak‐to‐valley ratio (>10⁵) due to the series resistance change of GeSe, MoS₂, and HJs at different gate voltages is observed. Moreover, strong and broad‐band photoresponse via the photoconductive effect are also demonstrated. The explored multifunctional properties of the GeSe/MoS₂ HJs are expected to be important for understanding the carrier transport and photoresponse of 2D‐material HJs for achieving their use in various new applications in the electronics and optoelectronics fields.     

A General Method for the Chemical Synthesis of Large‐Scale,Seamless Transition Metal Dichalcogenide Electronics

The capability to directly build atomically thin transition metal dichalcogenide (TMD) devices by chemical synthesis offers important opportunities to achieve large‐scale electronics and optoelectronics with seamless interfaces. Here, a general approach for the chemical synthesis of a variety of TMD (e.g., MoS₂, WS₂, and MoSe₂) device arrays over large areas is reported. During chemical vapor deposition, semiconducting TMD channels and metallic TMD/carbon nanotube (CNT) hybrid electrodes are simultaneously formed on CNT‐patterned substrate, and then coalesce into seamless devices. Chemically synthesized TMD devices exhibit attractive electrical and mechanical properties. It is demonstrated that chemically synthesized MoS₂–MoS₂/CNT devices have Ohmic contacts between MoS₂/CNT hybrid electrodes and MoS₂ channels. In addition, MoS₂–MoS₂/CNT devices show greatly enhanced mechanical stability and photoresponsivity compared with conventional gold‐contacted devices, which makes them suitable for flexible optoelectronics. Accordingly, a highly flexible pixel array based on chemically synthesized MoS₂–MoS₂/CNT photodetectors is applied for image sensing.     

Adjustable Intermolecular Interactions Allowing 2D Transition Metal Dichalcogenides with Prolonged Scavenging Activity for Reactive Oxygen Species

There is an increasing demand for control over the dimensions and functions of transition metal dichalcogenides (TMDs) in aqueous solution toward biological and medical applications. Herein, an approach for the exfoliation and functionalization of TMDs in water via modulation of the hydrophobic interaction between poly(ε‐caprolactone)‐b‐poly(ethylene glycol) (PCL‐b‐PEG) and the basal planes of TMDs is reported. Decreasing the hydrophobic PCL length of PCL‐b‐PEG from 5000 g mol^?1 (PCL₅₀₀₀) to 460 g mol^?1 (PCL₄₆₀) significantly increases the exfoliation efficiency of TMD nanosheets because the polymer–TMD hydrophobic interaction becomes dominant over the polymer–polymer interaction. The TMD nanosheets exfoliated by PCL₄₆₀‐b‐PEG₅₀₀₀ (460‐WS₂, 460‐WSe₂, 460‐MoS₂, and 460‐MoSe₂) show excellent and prolonged scavenging activity for reactive oxygen species (ROS), but each type of TMD displays a different scavenging tendency against hydroxyl, superoxide, and 2,2′‐azino‐bis(3‐ethylbenzothiazoline‐6‐sulfonic acid) radicals. A mechanistic study based on electron paramagnetic resonance spectroscopy and density functional theory simulations suggests that radical‐mediated oxidation of TMDs and hydrogen transfer from the oxidized TMDs to radicals are crucial steps for ROS scavenging by TMD nanosheets. As‐prepared 460‐TMDs are able to effectively scavenge ROS in HaCaT human keratinocytes, and also exhibit excellent biocompatibility.     

Graphene–Graphene Oxide Floating Gate Transistor Memory

A novel transparent, flexible, graphene channel floating‐gate transistor memory (FGTM) device is fabricated using a graphene oxide (GO) charge trapping layer on a plastic substrate. The GO layer, which bears ammonium groups (NH₃⁺), is prepared at the interface between the crosslinked PVP (cPVP) tunneling dielectric and the Al₂O₃ blocking dielectric layers. Important design rules are proposed for a high‐performance graphene memory device: i) precise doping of the graphene channel, and ii) chemical functionalization of the GO charge trapping layer. How to control memory characteristics by graphene doping is systematically explained, and the optimal conditions for the best performance of the memory devices are found. Note that precise control over the doping of the graphene channel maximizes the conductance difference at a zero gate voltage, which reduces the device power consumption. The proposed optimization via graphene doping can be applied to any graphene channel transistor‐type memory device. Additionally, the positively charged GO (GO–NH₃⁺) interacts electrostatically with hydroxyl groups of both UV‐treated Al₂O₃ and PVP layers, which enhances the interfacial adhesion, and thus the mechanical stability of the device during bending. The resulting graphene–graphene oxide FGTMs exhibit excellent memory characteristics, including a large memory window (11.7 V), fast switching speed (1 μs), cyclic endurance (200 cycles), stable retention (10⁵ s), and good mechanical stability (1000 cycles).     

Anisotropic MoS2 Nanosheets Grown on Self‐Organized Nanopatterned Substrates

Manipulating the anisotropy in 2D nanosheets is a promising way to tune or trigger functional properties at the nanoscale. Here, a novel approach is presented to introduce a one‐directional anisotropy in MoS₂ nanosheets via chemical vapor deposition (CVD) onto rippled patterns prepared on ion‐sputtered SiO₂/Si substrates. The optoelectronic properties of MoS₂ are dramatically affected by the rippled MoS₂ morphology both at the macro‐ and the nanoscale. In particular, strongly anisotropic phonon modes are observed depending on the polarization orientation with respect to the ripple axis. Moreover, the rippled morphology induces localization of strain and charge doping at the nanoscale, thus causing substantial redshifts of the phonon mode frequencies and a topography‐dependent modulation of the MoS₂ workfunction, respectively. This study paves the way to a controllable tuning of the anisotropy via substrate pattern engineering in CVD‐grown 2D nanosheets.     

Strong Coupling of MoS2 Nanosheets and Nitrogen‐Doped Graphene for High‐Performance Pseudocapacitance Lithium Storage

Layered material MoS₂ is widely applied as a promising anode for lithium‐ion batteries (LIBs). Herein, a scalable and facile dopamine‐assisted hydrothermal technique for the preparation of strongly coupled MoS₂ nanosheets and nitrogen‐doped graphene (MoS₂/N‐G) composite is developed. In this composite, the interconnected MoS₂ nanosheets are well wrapped onto the surface of graphene, forming a unique veil‐like architecture. Experimental results indicate that dopamine plays multiple roles in the synthesis: a binding agent to anchor and uniformly disperse MoS₂ nanosheets, a morphology promoter, and the precursor for in situ nitrogen doping during the self‐polymerization process. Density functional theory calculations further reveal that a strong interaction exists at the interface of MoS₂ nanosheets and nitrogen‐doped graphene, which facilitates the charge transfer in the hybrid system. When used as the anode for LIBs, the resulting MoS₂/N‐G composite electrode exhibits much higher and more stable Li‐ion storage capacity (e.g., 1102 mAh g^?1 at 100 mA g^?1) than that of MoS₂/G electrode without employing the dopamine linker. Significantly, it is also identified that the thin MoS₂ nanosheets display outstanding high‐rate capability due to surface‐dominated pseudocapacitance contribution.     

Pseudohalide‐Induced 2D (CH3NH3)2PbI2(SCN)2 Perovskite for Ternary Resistive Memory with High Performance

Recently, organic–inorganic hybrid perovskites (OIHP) are studied in memory devices, but ternary resistive memory with three states based on OIHP is not achieved yet. In this work, ternary resistive memory based on hybrid perovskite is achieved with a high device yield (75%), much higher than most organic ternary resistive memories. The pseudohalide‐induced 2D (CH₃NH₃)₂PbI₂(SCN)₂ perovskite thin film is prepared by using a one‐step solution method and fabricated into Al/perovskite film/indium–tin oxide (glass substrate as well as flexible polyethylene terephthalate substrate) random resistive access memory (RRAM) devices. The three states have a conductivity ratio of 1:10³:10⁷, long retention over 10 000 s, and good endurance properties. The electrode area variation, impedance test, and current–voltage plotting show that the two resistance switches are attributable to the charge trap filling due to the effect of unscreened defect in 2D nanosheets and the formation of conductive filaments, respectively. This work paves way for stable perovskite multilevel RRAMs in ambient atmosphere.     

Solvent‐Exchange Strategy toward Aqueous Dispersible MoS2 Nanosheets and Their Nitrogen‐Rich Carbon Sphere Nanocomposites for Efficient Lithium/Sodium Ion Storage

Major challenges in developing 2D transition‐metal disulfides (TMDs) as anode materials for lithium/sodium ion batteries (LIBs/SIBs) lie in rational design and targeted synthesis of TMD‐based nanocomposite structures with precisely controlled ion and electron transport. Herein, a general and scalable solvent‐exchange strategy is presented for uniform dispersion of few‐layer MoS₂ (f‐MoS₂) from high‐boiling‐point solvents (N‐methyl‐2‐pyrrolidone (NMP), N,N‐dimethyl formaldehyde (DMF), etc.) into low‐boiling‐point solvents (water, ethanol, etc.). The solvent‐exchange strategy dramatically simplifies high‐yield production of dispersible MoS₂ nanosheets as well as facilitates subsequent decoration of MoS₂ for various applications. As a demonstration, MoS₂‐decorated nitrogen‐rich carbon spheres (MoS₂‐NCS) are prepared via in situ growth of polypyrrole and subsequent pyrolysis. Benefiting from its ultrathin feature, largely exposed active surface, highly conductive framework and excellent structural integrity, the 2D core–shell architecture of MoS₂‐NCS exhibits an outstanding reversible capacity and excellent cycling performance, achieving high initial discharge capacity of 1087.5 and 508.6 mA h g^?1 at 0.1 A g^?1, capacity retentions of 95.6% and 94.2% after 500 and 250 charge/discharge cycles at 1 A g^?1, for lithium/sodium ion storages, respectively.     

Non‐Volatile Ferroelectric Memory with Position‐Addressable Polymer Semiconducting Nanowire

One‐dimensional nanowires (NWs) have been extensively examined for numerous potential nano‐electronic device applications such as transistors, sensors, memories, and photodetectors. The ferroelectric‐gate field effect transistors (Fe‐FETs) with semiconducting NWs in particular in combination with ferroelectric polymers as gate insulating layers have attracted great attention because of their potential in high density memory integration. However, most of the devices still suffer from low yield of devices mainly due to the ill‐control of the location of NWs on a substrate. NWs randomly deposited on a substrate from solution‐dispersed droplet made it extremely difficult to fabricate arrays of NW Fe‐FETs. Moreover, rigid inorganic NWs were rarely applicable for flexible non‐volatile memories. Here, we present the NW Fe‐FETs with position‐addressable polymer semiconducting NWs. Polymer NWs precisely controlled in both location and number between source and drain electrode were achieved by direct electrohydrodynamic NW printing. The polymer NW Fe‐FETs with a ferroelectric poly(vinylidene fluoride‐co‐trifluoroethylene) exhibited non‐volatile ON/OFF current margin at zero gate voltage of approximately 10² with time‐dependent data retention and read/write endurance of more than 10⁴ seconds and 10² cycles, respectively. Furthermore, our device showed characteristic bistable current hysteresis curves when being deformed with various bending radii and multiple bending cycles over 1000 times.     

Threshold Voltage Control of Multilayered MoS2 Field‐Effect Transistors via Octadecyltrichlorosilane and their Applications to Active Matrixed Quantum Dot Displays Driven by Enhancement‐Mode Logic Gates

In recent past, for next‐generation device opportunities such as sub‐10 nm channel field‐effect transistors (FETs), tunneling FETs, and high‐end display backplanes, tremendous research on multilayered molybdenum disulfide (MoS₂) among transition metal dichalcogenides has been actively performed. However, nonavailability on a matured threshold voltage control scheme, like a substitutional doping in Si technology, has been plagued for the prosperity of 2D materials in electronics. Herein, an adjustment scheme for threshold voltage of MoS₂ FETs by using self‐assembled monolayer treatment via octadecyltrichlorosilane is proposed and demonstrated to show MoS₂ FETs in an enhancement mode with preservation of electrical parameters such as field‐effect mobility, subthreshold swing, and current on–off ratio. Furthermore, the mechanisms for threshold voltage adjustment are systematically studied by using atomic force microscopy, Raman, temperature‐dependent electrical characterization, etc. For validation of effects of threshold voltage engineering on MoS₂ FETs, full swing inverters, comprising enhancement mode drivers and depletion mode loads are perfectly demonstrated with a maximum gain of 18.2 and a noise margin of ≈45% of 1/2 V_DD. More impressively, quantum dot light‐emitting diodes, driven by enhancement mode MoS₂ FETs, stably demonstrate 120 cd m^?2 at the gate‐to‐source voltage of 5 V, exhibiting promising opportunities for future display application.