WS2 Nanotube Transistor for Photodetection and Optoelectronic Memory Applications.

Nanotube and nanowire transistors hold great promises for future electronic and optoelectronic devices owing to their downscaling possibilities. In this work, a single multi-walled tungsten disulfide (WS2) nanotube is utilized as the channel of a back-gated field-effect transistor. The device exhibits a p-type behavior in ambient conditions, with a hole mobility µp ≈  1.4 cm2V-1s-1 and a subthreshold swing SS ≈ 10 V dec-1. Current-voltage characterization at different temperatures reveals that the device presents two slightly different asymmetric Schottky barriers at drain and source contacts. Self-powered photoconduction driven by the photovoltaic effect is demonstrated, and a photoresponsivity R ≈ 10 mAW-1 at 2 V drain bias and room temperature. Moreover, the transistor is tested for data storage applications. A two-state memory is reported, where positive and negative gate pulses drive the switching between two different current states, separated by a window of 130%. Finally, gate and light pulses are combined to demonstrate an optoelectronic memory with four well-separated states. The results herein presented are promising for data storage, Boolean logic, and neural network applications.

Mechanism of WS2 Nanotube Formation Revealed by in Situ/ex Situ Imaging.

Multiwall WS2 nanotubes have been synthesized from W18O49 nanowhiskers in substantial amounts for more than a decade. The established growth model is based on the "surface-inward" mechanism, whereby the high-temperature reaction with H2S starts on the nanowhisker surface, and the oxide-to-sulfide conversion progresses inward until hollow-core multiwall WS2 nanotubes are obtained. In the present work, an upgraded in situ SEM µReactor with H2 and H2S sources has been conceived to study the growth mechanism in detail. A hitherto undescribed growth mechanism, named "receding oxide core", which complements the "surface-inward" model, is observed and kinetically evaluated. Initially, the nanowhisker is passivated by several WS2 layers via the surface-inward reaction. At this point, the diffusion of H2S through the already existing outer layers becomes exceedingly sluggish, and the surface-inward reaction is slowed down appreciably. Subsequently, the tungsten suboxide core is anisotropically volatilized within the core close to its tips. The oxide vapors within the core lead to its partial out-diffusion, partially forming a cavity that expands with reaction time. Additionally, the oxide vapors react with the internalized H2S gas, forming fresh WS2 layers in the cavity of the nascent nanotube. The rate of the receding oxide core mode increases with temperatures above 900 °C. The growth of nanotubes in the atmospheric pressure flow reactor is carried out as well, showing that the proposed growth model (receding oxide core) is also relevant under regular reaction parameters. The current study comprehensively explains the WS2 nanotube growth mechanism, combining the known model with contemporary insight.

Addressing Irreversibility and Structural Distortion in WS2 Inorganic Fullerene-Like Nanoparticles: Effects of Voltage Cutoff Experiments in Beyond Li+-Ion Storage Applications.

Large interlayer spacing beneficially allows Na+- and K+-ion storage in transition-metal dichalcogenide (TMD)-based electrodes, but side reactions and volume change, which pulverize the TMD crystalline structure, are persistent challenges for the utilization of these materials in next-generation devices. This study first determines whether irreversibility due to structural distortion, which results in poor cycling stability, is also apparent in the case of inorganic fullerene-like (IF) tungsten disulfide (WS2) nanocages (WS2IF). To address these problems, this study proposes upper and lower voltage cutoff experiments to limit specific reactions in Na+/WS2IF and K+/WS2IF half-cells. Three-dimensional (3D) differential capacity curves and derived surface plots highlight the continuation of reversible reactions when a high upper cutoff technique is applied, thereby indirectly suggesting restricted structural dissolution. This resulted in improved capacity retention with stable performance and a higher Coulombic efficiency, laying the ground for the use of TMD-based materials beyond Li+-ion storage devices.

Implantation of Gallium into Layered WS2 Nanostructures is Facilitated by Hydrogenation.

Bombarding WS2 multilayered nanoparticles and nanotubes with focused ion beams of Ga+ ions at high doses, larger than 1016 cm-2 , leads to drastic structural changes and melting of the material. At lower doses, when the damage is negligible or significantly smaller, the amount of implanted Ga is very small. A substantial increase in the amount of implanted Ga, and not appreciable structural damage, are observed in nanoparticles previously hydrogenated by a radio-frequency activated hydrogen plasma. Density functional calculations reveal that the implantation of Ga in the spaces between adjacent layers of pristine WS2 nanoparticles is difficult due to the presence of activation barriers. In contrast, in hydrogenated WS2 , the hydrogen molecules are able to intercalate in between adjacent layers of the WS2 nanoparticles, giving rise to the expansion of the interlayer distances, that in practice leads to the vanishing of the activation barrier for Ga implantation. This facilitates the implantation of Ga atoms in the irradiation experiments.

0D van der Waals interfacial ferroelectricity.

The dimensional limit of ferroelectricity has been long explored. The critical contravention is that the downscaling of ferroelectricity leads to a loss of polarization. This work demonstrates a zero-dimensional ferroelectricity by the atomic sliding at the restrained van der Waals interface of crossed tungsten disufilde nanotubes. The developed zero-dimensional ferroelectric diode in this work presents not only non-volatile resistive memory, but also the programmable photovoltaic effect at the visible band. Benefiting from the intrinsic dimensional limitation, the zero-dimensional ferroelectric diode allows electrical operation at an ultra-low current. By breaking through the critical size of depolarization, this work demonstrates the ultimately downscaled interfacial ferroelectricity of zero-dimensional, and contributes to a branch of devices that integrates zero-dimensional ferroelectric memory, nano electro-mechanical system, and programmable photovoltaics in one.

Submillimeter-Long WS2 Nanotubes: The Pathway to Inorganic Buckypaper.

WS2 nanotubes present many new technologies under development, including reinforced biocompatible polymers, membranes, photovoltaic-based memories, ferroelectric devices, etc. These technologies depend on the aspect ratio (length/diameter) of the nanotubes, which was limited to 100 or so. A new synthetic technique is presented, resulting in WS2 nanotubes a few hundred micrometers long and diameters below 50 nm (aspect ratios of 2000-5000) in high yields. Preliminary investigation into the mechanistic aspects of the two-step synthesis reveals that W5O14 nanowhisker intermediates are formed in the first step of the reaction instead of the ubiquitous W18O49 nanowhiskers used in the previous syntheses. The electrical and photoluminescence properties of the long nanotubes were studied. WS2 nanotube-based paper-like material was prepared via a wet-laying process, which could not be realized with the 10 µm long WS2 nanotubes. Ultrafiltration of gold nanoparticles using the nanotube-paper membrane was demonstrated.

Silane functionalization of WS2 nanotubes for interaction with poly(lactic acid).

Functionalisation of nanofillers is required for the promotion of strong interfacial interactions with polymers and is essential as a route for the preparation of (nano)composites with superior mechanical properties. Tungsten disulphide nanotubes (WS2 NTs) were functionalized using (3-aminopropyl) triethoxysilane (APTES) for preparation of composites with poly(lactic acid) (PLA). The WS2 NTs : APTES ratios used were 1 : 1, 1 : 2 and 1 : 4 WS2 NTs : APTES. The APTES formed siloxane networks bound to the NTs via surface oxygen and carbon moieties adsorbed on the WS2 NTs surface, detected by X-ray photoelectron spectroscopy (XPS) studies and chemical mapping using energy dispersive X-ray spectroscopy in the scanning transmission electron microscope (STEM-EDS). The successful silane modification of the WS2 NTs was clearly evident with both significant peak shifting by as much as 60 cm-1 for Si-O-Si vibrations (FTIR) and peak broadening of the A1g band in the Raman spectra of the WS2 NTs. The evolution of new bands was also observed and are associated with Si-CH2-CH2 and, symmetric and assymetric -NH3+ deformation modes (FTIR). Further evidence for functionalization was obtained from zeta potential measurements as there was a change in surface charge from negative for pure WS2 NTs to positive for APTES modified WS2 NTs. Additionally, the thermal stability of APTES was shifted to much higher temperatures as it was bound to the WS2 NTs. The APTES modified WS2 NTs were organophilic and readily dispersed in PLA, while presence of the pendant amine and hydroxyl groups resulted in strong interfacial interactions with the polymer matrix. The inclusion of as little as 0.5 wt% WS2 NTs modified with 2.0 wt% APTES resulted in an increase of 600% in both the elongation at break (a measure of ductility) and the tensile toughness relative to neat PLA, without impacting the stiffness or strength of the polymer.

WS2 Nanotube-Embedded SiOC Fibermat Electrodes for Sodium-Ion Batteries.

Layered transition metal dichalcogenides (TMDs) such as tungsten disulfide (WS2) are promising materials for a wide range of applications, including charge storage in batteries and supercapacitors. Nevertheless, TMD-based electrodes suffer from bottlenecks such as capacity fading at high current densities, voltage hysteresis during the conversion reaction, and polysulfide dissolution. To tame such adverse phenomena, we fabricate composites with WS2 nanotubes. Herein, we report on the superior electrochemical performance of ceramic composite fibers comprising WS2 nanotubes (WS2NTs) embedded in a chemically robust molecular polymer-derived ceramic matrix of silicon-oxycarbide (SiOC). Such a heterogeneous fiber structure was obtained via electrospinning of WS2NT/preceramic polymer solution followed by pyrolysis at elevated temperatures. The electrode capacity fading in WS2NTs was curbed by the synergistic effect between WS2NT and SiOC. As a result, the composite electrode exhibits high initial capacity of 454 mAh g-1 and the capacity retention approximately 2-3 times higher than that of the neat WS2NT electrode.

Improved Electrochemical Performance of NTs-WS2@C Nanocomposites for Lithium-Ion and Sodium-Ion Batteries.

Even though WS2 nanotubes (NTs-WS2) have great potential as anode materials for lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs) thanks to their unusual layered structure, their conductivity and cycling stability are far from satisfactory. To tackle these issues, carbon-coated WS2 (NTs-WS2@C) nanocomposites were prepared through a facile synthesis method that involved precipitating a carbon precursor (20% sucrose) on WS2 nanotubes, followed by annealing treatment under an argon environment. Thanks to the presence of highly conductive and mechanically robust carbon on the outer surface, NTs-WS2@C nanocomposites show improved electrochemical performance compared with bare NTs-WS2. After 60 cycles at 80 mA g-1 current density, the cells display high capacities of 305 mAh g-1 in LIBs and 152 mAh g-1 in SIBs, respectively. As the current density increases to 600 mA g-1, it provides specific capacities of 209 and 115 mAh g-1, correspondingly. The enhanced electrochemical performance in LIBs and SIBs is primarily attributed to the synergistic effects of the tubular architecture of WS2, carbon network and stable nanocomposite structure, which can effectively constrain volume variation during the metal ions intercalation/deintercalation processes.

Mesoscopic sliding ferroelectricity enabled photovoltaic random access memory for material-level artificial vision system.

Intelligent materials with adaptive response to external stimulation lay foundation to integrate functional systems at the material level. Here, with experimental observation and numerical simulation, we report a delicate nano-electro-mechanical-opto-system naturally embedded in individual multiwall tungsten disulfide nanotubes, which generates a distinct form of in-plane van der Waals sliding ferroelectricity from the unique combination of superlubricity and piezoelectricity. The sliding ferroelectricity enables programmable photovoltaic effect using the multiwall tungsten disulfide nanotube as photovoltaic random-access memory. A complete "four-in-one" artificial vision system that synchronously achieves full functions of detecting, processing, memorizing, and powering is integrated into the nanotube devices. Both labeled supervised learning and unlabeled reinforcement learning algorithms are executable in the artificial vision system to achieve self-driven image recognition. This work provides a distinct strategy to create ferroelectricity in van der Waals materials, and demonstrates how intelligent materials can push electronic system integration at the material level.

Size and Shape's Effects on the High-Pressure Behavior of WS2 Nanomaterials.

Exploring the behavior of nanocrystals with varying shapes and sizes under high pressure is crucial to understanding the relationship between the morphology and properties of nanomaterials. In this study, we investigated the compression behaviors of WS2 nanotubes (NT-WS2) and fullerene-like nanoparticles (IF-WS2) by in situ high-pressure X-ray diffraction (XRD) and Raman spectroscopy. It was found that the bulk modulus of NT-WS2 is 81.7 GPa, which is approximately twice as large as that of IF-WS2 (46.3 GPa). This might be attributed to the fact that IF-WS2 with larger d-spacing along the c-axis and higher defect density are more compressible under isotropic pressure than NT-WS2. Thus, the slender NT-WS2 possess a more stable crystal structure than the IF-WS2. Our findings reveal that the effects of morphology and size play crucial roles in determining the high-pressure properties of WS2 nanoparticles, and provide significant insight into the relationship between structure and properties.

Poly(L-lactic acid) Reinforced with Hydroxyapatite and Tungsten Disulfide Nanotubes.

Poly(L-lactic acid) (PLLA) is a biocompatible, biodegradable, and semi-crystalline polymer with numerous applications including food packaging, medical implants, stents, tissue engineering scaffolds, etc. Hydroxyapatite (HA) is the major component of natural bone. Conceptually, combining PLLA and HA could produce a bioceramic suitable for implants and bone repair. However, this nanocomposite suffers from poor mechanical behavior under tensile strain. In this study, films of PLLA and HA were prepared with small amounts of nontoxic WS2 nanotubes (INT-WS2). The structural aspects of the films were investigated via electron microscopy, X-ray diffraction, Raman microscopy, and infrared absorption spectroscopy. The mechanical properties were evaluated via tensile measurements, micro-hardness tests, and nanoindentation. The thermal properties were investigated via differential scanning calorimetry. The composite films exhibited improved mechanical and thermal properties compared to the films prepared from the PLLA and HA alone, which is advantageous for medical applications.

Interaction of Poly L-Lactide and Tungsten Disulfide Nanotubes Studied by in Situ X-ray Scattering during Expansion of PLLA/WS2NT Nanocomposite Tubes.

In situ synchrotron X-ray scattering was used to reveal the transient microstructure of poly(L-lactide) (PLLA)/tungsten disulfide inorganic nanotubes (WS2NTs) nanocomposites. This microstructure is formed during the blow molding process ("tube expansion") of an extruded polymer tube, an important step in the manufacturing of PLLA-based bioresorbable vascular scaffolds (BVS). A fundamental understanding of how such a microstructure develops during processing is relevant to two unmet needs in PLLA-based BVS: increasing strength to enable thinner devices and improving radiopacity to enable imaging during implantation. Here, we focus on how the flow generated during tube expansion affects the orientation of the WS2NTs and the formation of polymer crystals by comparing neat PLLA and nanocomposite tubes under different expansion conditions. Surprisingly, the WS2NTs remain oriented along the extrusion direction despite significant strain in the transverse direction while the PLLA crystals (c-axis) form along the circumferential direction of the tube. Although WS2NTs promote the nucleation of PLLA crystals in nanocomposite tubes, crystallization proceeds with largely the same orientation as in neat PLLA tubes. We suggest that the reason for the unusual independence of the orientations of the nanotubes and polymer crystals stems from the favorable interaction between PLLA and WS2NTs. This favorable interaction leads WS2NTs to disperse well in PLLA and strongly orient along the axis of the PLLA tube during extrusion. As a consequence, the nanotubes are aligned orthogonally to the circumferential stretching direction, which appears to decouple the orientations of PLLA crystals and WS2NTs.

Probing the Chiral Domains and Excitonic States in Individual WS2 Tubes by Second-Harmonic Generation.

Distinct from carbon nanotubes, transition-metal dichalcogenide (TMD) nanotubes are noncentrosymmetric and polar and can exhibit some intriguing phenomena such as nonreciprocal superconductivity, chiral shift current, bulk photovoltaic effect, and exciton-polaritons. However, basic characterizations of individual TMD nanotubes are still quite limited, and much remains unclear about their structural chirality and electronic properties. Here we report an optical second-harmonic generation (SHG) study on multiwalled WS2 nanotubes on a single-tube level. As it is highly sensitive to the crystallographic symmetry, SHG microscopy unveiled multiple structural domains within a single WS2 nanotube, which are otherwise hidden under conventional white-light optical microscopy. Moreover, the polarization-resolved SHG anisotropy patterns revealed that different domains on the same tube can be of different chirality. In addition, we observed the excitonic states of individual WS2 nanotubes via SHG excitation spectroscopy, which were otherwise difficult to acquire due to the indirect band gap of the material.

WS2 Nanotubes: Electrical Conduction and Field Emission Under Electron Irradiation and Mechanical Stress.

This study reports the electrical transport and the field emission properties of individual multi-walled tungsten disulphide (WS2 ) nanotubes (NTs) under electron beam irradiation and mechanical stress. Electron beam irradiation is used to reduce the nanotube-electrode contact resistance by one-order of magnitude. The field emission capability of single WS2 NTs is investigated, and a field emission current density as high as 600 kA cm-2 is attained with a turn-on field of ≈100 V µm-1 and field-enhancement factor ≈50. Moreover, the electrical behavior of individual WS2 NTs is studied under the application of longitudinal tensile stress. An exponential increase of the nanotube resistivity with tensile strain is demonstrated up to a recorded elongation of 12%, thereby making WS2 NTs suitable for piezoresistive strain sensor applications.

Solving the "MoS2 Nanotubes" Synthetic Enigma and Elucidating the Route for Their Catalyst-Free and Scalable Production.

This study solves a more than two-decades-long "MoS2 Nanotubes" synthetic enigma: the futile attempts to synthesize inorganic nanotubes (INTs) of MoS2 via vapor-gas-solid (VGS) reaction. Among them was replication of the recently reported pure-phase synthesis of the analogous INT-WS2. During these years, successful syntheses of spherical nanoparticles of WS2 and MoS2 were demonstrated as well. All these nanostructures were obtained by VGS reaction of corresponding oxides with H2/H2S gases, at elevated temperatures (>800 °C), in a fluidized bed reactor (FBR) and a one-pot process. This success and apparent similarity between the two compounds "hid" from us the option of looking for the INT-MoS2 reaction parameters in entirely different regimes. The main challenge in the synthesis of INT-MoS2 via VGS was the instability of the in situ prepared suboxide nanowhiskers against over-reduction and recrystallization at high temperatures. The elucidated growth mechanism dictates separation of the reaction into five steps, as properties of the intermediate products are not consistent with a single process and require individual conditions for each step. A horizontal reactor with a porous-quartz reaction cell, which creates proper quasi-static (contrary to the FBR) conditions for the reaction involving sublimation, was imperative for the effective nanofabrication of INT-MoS2. These findings render a reproducible synthetic route for the production of highly crystalline pure-phase MoS2 nanotubes via a multistep VGS process, without the assistance of a catalyst and in a scalable fashion. Being a semiconductor, flexible, and strong, INT-MoS2 offers a platform for much research and numerous potential applications, particularly in the field of optoelectronics and reinforcement of polymer composites.

Size-Dependent Control of Exciton-Polariton Interactions in WS2 Nanotubes.

Multiwall WS2 nanotubes (and fullerene-like nanoparticles thereof) are currently synthesized in large amounts, reproducibly. Other than showing interesting mechanical and tribological properties, which offer them a myriad of applications, they are recently shown to exhibit remarkable optical and electrical properties, including quasi-1D superconductivity, electroluminescence, and a strong bulk photovoltaic effect. Here, it is shown that, using a simple dispersion-fractionation technique, one can control the diameter of the nanotubes and move from pure excitonic to polaritonic features. While nanotubes of an average diameter >80 nm can support cavity modes and scatter light effectively via a strong coupling mechanism, the extinction of nanotubes with smaller diameter consists of pure absorption. The experimental work is complemented by finite-difference time-domain simulations, which shed new light on the cavity mode-exciton interaction in 2D materials. Furthermore, transient absorption experiments of the size-fractionated nanotubes fully confirm the steady-state observations. Moreover, it is shown that the tools developed here are useful for size control of the nanotubes, e.g., in manufacturing environment. The tunability of the light-matter interaction of such nanotubes offers them intriguing applications such as polaritonic devices, in photocatalysis, and for multispectral sensors.

Diameter-Dependent Superconductivity in Individual WS2 Nanotubes.

Transition metal dichalcogenide nanotubes are fascinating platforms for the research of superconductivity due to their unique dimensionalities and geometries. Here we report the diameter dependence of superconductivity in individual WS2 nanotubes. The superconductivity is realized by electrochemical doping via the ionic gating technique in which the diameter of the nanotube is estimated from the periodic oscillating magnetoresistance, known as the Little-Parks effect. The critical temperature of superconductivity displays an unexpected linear behavior as a function of the inverse diameter, that is, the curvature of the nanotube. The present results are an important step in understanding the microscopic mechanism of superconductivity in a nanotube, opening up a new way of superconductivity in crystalline nanostructures.

Modelling of adsorption and intercalation of hydrogen on/into tungsten disulphide multilayers and multiwall nanotubes.

Understanding the interaction of hydrogen with layered materials is crucial in the fields of sensors, catalysis, fuel cells and hydrogen storage, among others. Density functional theory, improved by the introduction of van der Waals dispersion forces, provides an efficient and practical workbench to investigate the interaction of molecular and atomic hydrogen with WS2 multilayers and nanotubes. We find that H2 physisorbs on the surface of those materials on top of W atoms, while atomic H chemisorbs on top of S atoms. In the case of nanotubes, the chemisorption strength is sensitive to the nanotube diameter. Diffusion of H2 on the surface of WS2 encounters quite small activation barriers whose magnitude helps to explain previous and new experimental results for the observed dependence of the hydrogen concentration with temperature. Intercalation of H2 between adjacent planar WS2 layers reveals an endothermic character. Intercalating H atoms is energetically favorable, but the intercalation energy does not compensate for the cost of dissociating the molecules. When H2 molecules are intercalated between the walls of a double wall nanotube, the rigid confinement induces the dissociation of the confined molecules. A remarkable result is that the presence of a full H2 monolayer adsorbed on top of the first WS2 layer of a WS2 multilayer system strongly facilitates the intercalation of H2 between WS2 layers underneath. This opens up an additional gate to intercalation processes.

Raman scattering from single WS2 nanotubes in stretched PVDF electrospun fibers.

Inorganic WS2 nanotubes (INT-WS2) were embedded into sub-µm polyvinylidene fluoride-co-hexafluropropylene (PVDF-HFP) electrospun fibers. In this report we explore the Raman scattering spectroscopy from a single nanotube during stretching of individual nanocomposite fibers. Red shifts of up to ∼4.7 cm-1 for A1g and E WS2 bands were found before reaching the "tearing point" of the fibers. These shifts may correlate with up to ∼2.8% of the WS2 nanotube elongation. Moreover, the absence of the A1g and E bands' broadening, as well as the nonappearance of the E shear mode in the nanotube Raman spectra, suggest the stretching of the nanotubes as a whole (including inner layers). These results point to the excellent adhesion of the nanotubes' surface to the polymer and to the effective load transfer from the polymer to the WS2 nanotube. In order to elucidate the nature of interaction between the polymer and the nanofiller, we modeled the deformation of composite fibers using an elastic lattice spring model (LSM). The results of the model are fully consistent with our interpretation.