Transforming friction: unveiling sliding-induced phase transitions in CVD-grown WS2 monolayers under single-asperity sliding nanocontacts.

Transition metal dichalcogenides (TMDs) exhibit diverse properties across different phases, making them promising materials for various engineering applications. In the present work, we employed a comprehensive approach, combining experimental investigations and computational simulations to elucidate the remarkable tunable frictional characteristics of chemical vapor deposition (CVD) grown WS2 monolayers through the sliding-induced transitions between the 1H and 1T' phases. Our atomic force microscopy (AFM) measurements reveal a significant contrast in friction between the two phases, with the 1H phase displaying higher friction (∼52%) than the 1T' phase. Surprisingly, under repeated scanning at constant stress, the friction of the 1H phase decreases, eventually matching the lower friction values of the 1T' phase. It was observed that the phase transformation is irreversible and is strongly dependent on contact stresses and is accelerated as the contact stress is increased by increasing the applied normal load. Molecular dynamics (MD) simulations provide further insights into the phase transition mechanism, highlighting the role of localized lateral stress and strain induced by sliding an AFM tip on the 1H phase. The simulations confirm that sliding induced localized lateral strain plays a crucial role in the phase transition, ultimately resulting in a decrease in friction. Moreover, our simulations unveil an intriguing connection between friction, potential energy surfaces, and the localized lateral strain during the phase transformation process. Our findings not only offer insights into the tribological properties of TMD materials but also open new possibilities for tailoring their performance in various applications where reducing friction and wear is crucial.

Disinfection by-products control in wastewater effluents treated with ozone and biological activated carbon followed by UV/Chlor(am)ine processes.

Sequential utilization of ozone (O3) and biological activated carbon (BAC) followed by UV/chlor(am)ine advanced oxidation process (AOP) has drawn attention in water reuse. However, the formation of disinfection by-products (DBPs) in this process is less evaluated. This study investigated the DBP formation and the relevant toxicity during the O3-BAC-UV/chlor(am)ine treatment of sand-filtered municipal secondary effluent. DBP formation in UV/chlorine and UV/dichloramine (NHCl2) processes were compared, where the impact of key operational parameters (e.g., UV wavelength, pH) on DBP formation were comprehensively evaluated. O3-BAC significantly reduced DBP formation potential (DBPFP) (58.2 %). Compared to UV/chlorine AOP, UV/NHCl2 AOP reduced DBP formation by 29.7 % in short-time treatment, while insignificantly impacting on DBPFP (p > 0.05). UV/NHCl2 AOP also led to lower calculated cytotoxicity (67.7 %) and genotoxicity (55.9 %) of DBPs compared to UV/chlorine AOP. Compared to 254 nm UV light, the utilization of 285 nm UV light decreased the formation of DBPs in wastewater treated with the UV/chlorine AOP and UV/NHCl2 AOP by 31.3 % and 19.2 %, respectively. However, the cytotoxicity and genotoxicity in UV/NHCl2 AOP using 285 nm UV light increased by 83.4 % and 58.5 %, respectively, compared to 254 nm. The concentration of DBPs formed in the UV/NHCl2 AOP at pH 8 was 54.3 % lower than that at pH 7, suggesting a better control of DBPs at alkaline condition. In the presence of bromide, UV/NHCl2 AOP tended to generate more brominated DBPs than UV/chlorine AOP. Overall, UV/NHCl2 AOP resulted in lower concentration and toxicity of DBPs compared to UV/chlorine AOP.

Paper based flexible MoS2-CNT hybrid memristors.

We report for the first time MoS2/CNT hybrid nanostructures for memristor applications on flexible and bio-degradable cellulose paper. In our approach, we varied two different weight percentages (10% and 20%) of CNT's in MoS2to improve the MoS2conductivity and investigate the memristor device characteristics. The device with 10% CNT shows a lowVSETvoltage of 2.5 V, which is comparatively small for planar devices geometries. The device exhibits a long data retention time and cyclic current-voltage stability of ∼104s and 102cycles, making it a potential candidate in flexible painted electronics. Along with good electrical performance, it also demonstrates a high mechanical stability for 1000 bending cycles. The conduction mechanism in the MoS2-CNT hybrid structure is corroborated by percolation and defect-induced filament formation. Additionally, the device displays synaptic plasticity performance, simulating potentiation and depression processes. Furthermore, such flexible and biodegradable cellulose-based paper electronics may pave the way to address the environmental pollution caused by electronic waste in the near future.

Substrate Versatile Roller Ball Pen Writing of Nanoporous MoS2 for Energy Storage Devices.

Low-cost fabrication of customizable supercapacitors and batteries to power up portable electronic devices is a much-needed step in advancing energy storage devices. The processing methods and techniques involved in developing small-sized entities in complex patterns are expensive, tedious, and time-consuming. Here, we demonstrate the fabrication of customizable electrochemical supercapacitors and batteries by simply employing the universal and conventional paradigm of direct pen writing with hands and evaluating their energy storage performance. The fabrication technique involves the refilling of MoS2 ink into the pen and then scripting of MoS2 nanostructures onto various substrates. The electrode material employed here consists of nanoporous microspheres of MoS2 synthesized by a simple one-step hydrothermal method. Direct pen writing with porous MoS2 in complex patterns enables easy, affordable, and simple fabrication of energy storage devices as and when required based on user choice toward distributed manufacturing and sustainability.

Porosity-Engineered CNT-MoS2 Hybrid Nanostructures for Bipolar Supercapacitor Applications.

Bipolar supercapacitors that can store many fold higher capacitance in negative voltage compared to positive voltage are of great importance if they can be engineered for practical applications. The electrode material encompassing high surface area, better electrochemical stability, high conductivity, moderate distribution of pore size, and their interaction with suitable electrolytes is imperative to enable bipolar supercapacitor performance. Apropos of the aforementioned aspects, the intent of this work is to ascertain the effect of ionic properties of different electrolytes on the electrochemical properties and performance of a porous CNT-MoS2 hybrid microstructure toward bipolar supercapacitor applications. The electrochemical assessment reveals that the CNT-MoS2 hybrid electrode exhibited a two- to threefold higher areal capacitance value of 122.3 mF cm-2 at 100 µA cm-2 in 1 M aqueous Na2SO4 and 42.13 mF cm-2 at 0.30 mA cm-2 in PVA-Na2SO4 gel electrolyte in the negative potential window in comparison to the positive potential window. The CNT-MoS2 hybrid demonstrates a splendid Coulombic efficiency of ∼102.5% and outstanding stability with capacitance retention showing a change from 100% to ∼180% over 7000 repeated charging-discharging cycles.

Arresting the surface oxidation kinetics of bilayer 1T'-MoTe2by sulphur passivation.

MoTe2garnered much attention among 2D materials due to stable polymorphs with distinctive structural and electronic properties. Among the polymorphs, 1T'-MoTe2in bulk form is type-II Weyl semimetal while, in monolayer form is a quantum spin Hall insulator. Thus, it is suitable for a wide variety of applications. Nevertheless, 1T'-MoTe2degrades within a few hours when exposed to the atmosphere and causes hindrances in device fabrication. Here the degradation kinetics of CVD-synthesized 1T'-MoTe2was investigated using Raman spectroscopy, XPS, and microscopic characterizations. The degradation rate of as-grown 1T'-MoTe2obtained was 9.2 × 10-3min-1. Further, we prevented the degradation of 1T'-MoTe2by introducing a thin coating of S that encapsulates the flakes. 1T'-MoTe2flakes showed stability for several days when covered using sulphur, indicating 25 times enhanced structural stability.

Nanoscale friction and wear behavior of a CVD-grown aged WS2 monolayer: the role of wrinkles and surface chemistry.

Friction reduction by transition metal dichalcogenide (TMD) monolayers is well documented; however, wrinkle formation on the surface of TMDs takes place due to strain relaxation over time and leads to the deterioration of the tribological properties at a small scale. Herein, we report the role of wrinkles on the wear behavior of a chemical vapor deposition (CVD) grown aged WS2 monolayer and the comparison with wrinkle-free regions. Atomic force microscopy (AFM) was utilized to perform load-dependent experiments, and we noticed that the wear initiated near wrinkles resulted in the disintegration of the monolayer. In contrast, in the wrinkle-free regions, wear occurred at significantly higher loads, similar to that of freshly grown WS2, although the coefficient of friction (COF) was increased due to the changes in surface chemistry as a result of aging, which was confirmed using X-ray photoelectron spectroscopy (XPS). In the presence of wrinkles, a ten-fold reduction in the load-carrying capacity was observed compared to the wrinkle-free regions. Molecular dynamics (MD) simulations were used to corroborate experimental findings, which demonstrate the role of wrinkles in the initiation of wear due to the stress concentration under sliding nanocontacts near the wrinkles. In addition, simulations help establish a relationship between the adsorbed chemical species on the surface and increased COF.

Heteroatomic stitching of broken WS2 monolayer with enhanced surface potential.

Sub-nanometre thick two-dimensional (2D) materials suffer from severe cracking during the high temperature chemical vapour deposition growth process. The cracking can be utilised to generate more active edges. These active edges can be stitched with a homo- or hetero-material. While the direct growth of 2D-heterostructures is mostly limited to a small fraction of outer edges of monolayer flakes, the cracked monolayers can be utilised to produce a large fraction of heterostructures. Heterostructures are important for developing multifunctional components for nanoscale electronics and optoelectronics. In this work, we demonstrate the formation of WS2-MoS2 heterostructures in large fractions by atomic stitching of cracked WS2 monolayers with the sequential growth of MoS2. Aberration-corrected scanning transmission electron microscopy and Raman spectroscopy have been utillised to probe fine details on the stitched interface between WS2 and MoS2. Growth of MoS2 domains were observed to take place at the terminating edge of cracked WS2, which then merged to form MoS2 multilayers at the cracked site. Growth of MoS2 at the opposite edges of WS2 eventually results in a MoS2-MoS2 junction with a Σ = 7 tilt boundary. Kelvin probe force microscope (KPFM) measurement from the stitched region revealed that the work function of WS2 is ∼32.46 meV higher than that of MoS2, which also closely matches with the Fermi energy difference between these two materials. With the aid of an atomic force microscope and KPFM, the surface potential width at the stitched region was found to be ∼5 times higher than the actual width of the interface, confirming the modulation of properties near the interface.

Fabrication of vertically aligned CNT- vanadium oxide hybrid architecture with enhanced compressibility and supercapacitor performance.

The demand for energy storage devices in wearable electronics effectuates a requisition for compressible and flexible supercapacitors with high performance and mechanical reliability. We report the fabrication of vanadium oxide hybrid with VACNT and its electrochemical supercapacitor performance along with the compression response. Compressive modulus of 730 ± 40 kPa is obtained for bare VACNT forest whereas its hybrid with vanadium oxide shows a compressive modulus of 240 ± 60 kPa. Controlled CVD process enabled the formation of porous CNT architecture coated with vanadium oxide particles due to the simultaneous reduction of V2O5and partial oxidation of CNT forest. Vanadium oxide decorated on vertically aligned carbon nanotubes acts as the active material for supercapacitor applications. A 17 folds increase in areal capacitance and 36 folds increase in volumetric capacitance are observed on depositing vanadium oxide particles on the VACNT forest. High coulombic efficiency of 97.8% is attained even after 10 000 charge-discharge cycles indicating the high stability of the hybrid.

Interplay between Thermal Stress and Interface Binding on Fracture of WS2 Monolayer with Triangular Voids.

The defect engineering of two-dimensional (2D) materials has become a pivotal strategy for tuning the electrical and optical properties of the material. However, the reliable application of these atomically thin materials in practical devices require careful control of structural defects to avoid premature failure. Herein, a systematic investigation is presented to delineate the complex interactions among structural defects, the role of thermal mismatch between WS2 monolayer and different substrates, and their consequent effect on the fracture behavior of the monolayer. Detailed microscopic and Raman/PL spectroscopic observations enabled a direct correlation between thermal mismatch stress and crack patterns originating from the corner of faceted voids in the WS2 monolayer. Aberration-corrected STEM-HAADF imaging reveals the tensile strain localization around the faceted void corners. Density functional theory (DFT) simulations on interfacial interaction between the substrate (Silicon and sapphire -Al2O3) and monolayer WS2 revealed a binding energy between WS2 and Si substrate is 20 times higher than that with a sapphire substrate. This increased interfacial interaction in WS2 and substrate-aided thermal mismatch stress arising due to difference in thermal expansion coefficient to a maximum extent leading to fracture in monolayer WS2. Finite element simulations revealed the stress distribution near the void in the WS2 monolayer, where the maximum stress was concentrated at the void tip.

A light-fostered supercapacitor performance of multi-layered ReS2 grown on conducting substrates.

The light-fostered supercapacitor performance introduces a new realm in the field of smart energy storage applications. Transition metal dichalcogenides (TMDCs) with direct band gap are intriguing candidates for developing a light-induced supercapacitor that can enhance energy storage when shined with light. Many TMDCs show a transition from a direct to indirect band gap as the layer number increases, while ReS2 possesses a direct band gap in both bulk and monolayer forms. The growth of such multi-layered 2D materials with high surface area on conducting substrates makes them suitable for smart energy storage applications with the ability to tune their performance with light irradiation. In this report, we present the growth of vertically aligned multi-layered ReS2 with large areal coverage on various conducting and non-conducting substrates, including stainless steel via chemical vapor deposition (CVD). To investigate the effect of light illumination on the charge storage performance, electrochemical measurements have been performed in dark and light conditions. Cyclic voltammetry (CV) curves showed an increase in the area enclosed by the curve, manifesting the increased charge storage capacity under light illumination as compared to dark. The volumetric capacitance value calculated from charging-discharging curves has increased from 17.9 F cm-3 to 29.8 F cm-3 with the irradiation of light for the as-grown ReS2 on a stainless steel plate. More than 1.5 times the capacitance enhancement is attributed to excess electron-hole pairs generated upon light illumination, contributing to the charge storage in the presence of light. The electrochemical impedance spectroscopy further augments these results. The high cyclic stability is attained with a capacitance retention value of 81% even after 10 000 repeated charging-discharging cycles.

Fabrication of iron oxide-CNT based flexible asymmetric solid state supercapacitor device with high cyclic stability.

Integration of high surface area nanostructures with conducting and deformable electrodes at large scale are of significant importance for flexible supercapacitors with high cyclic stability and low cost. Here, we report water assisted meter scale growth of aligned iron oxide and CNT 1D nanostructures on flexible stainless steel mesh for asymmetric supercapacitor device applications. Electron microscopic investigations revealed the uniform coverage of both iron oxide and CNT forest nanostructures over one meter length of SS mesh. Both iron oxide and CNT nanostructures were tested for supercapacitor electrode material in neutral electrolytes. Further, asymmetric solid state devices were fabricated and connected in serial fashion to demonstrate glowing of LEDs as well as rotation of 5 V micro fan. In addition, at bending angle of 90°, device showed 68% increase whereas, at 180° it showed 13% decrease in capacitance. The calculated specific capacitance for single device is found to be 14.4 mF cm-2. Corresponding energy density and power density are found to be 3 µW-hr cm-2 and 0.74 mW cm-2 respectively. The device showed remarkable capacitance retention of 87% over 25 000 charge discharge cycles. The flexible nature with remarkable cyclic stability of solid state iron oxide/CNT device is suitable for low cost flexible and wearable supercapacitor applications.

Thermal expansion coefficient and phonon dynamics in coexisting allotropes of monolayer WS2 probed by Raman scattering.

We report a comprehensive temperature dependent Raman measurement on three different phases of monolayer WS2 from 4 K to 330 K in a wide spectral range. Our studies reveal the anomalous nature of the first, as well as the higher order combination modes reflected in the disappearance of the few modes and anomalous temperature evaluation of the phonon self-energy parameters attributed to the detuning of resonance condition and development of strain due to thermal expansion mismatch with the underlying substrate. Our detailed temperature dependence studies also decipher the ambiguity about the assignment of the two modes in literature near ~297 cm-1 and 325 cm-1. The mode near 297 cm-1 is assigned as [Formula: see text] first order Raman mode, which is forbidden in the backscattering geometry, and 325 cm-1 is assigned to the combination of [Formula: see text] and [Formula: see text] mode. We also estimated thermal expansion coefficient by systematically disentangling the substrate effect in the temperature range of 4 K to 330 K and probed its temperature dependence in the 1H, 1T and 1T' phases.

Scalable faceted voids with luminescent enhanced edges in WS2 monolayers.

A scalable approach is needed in the formation of atomically flat edges with specific terminations to enhance local properties for optoelectronic, nanophotonic and energy applications. We demonstrate point defect clustering-driven faceted void formations with luminescent enhanced edges in WS2 monolayers during large-scale CVD growth and controlled annealing. With the aid of aberration-corrected scanning transmission electron microscopy (AC-STEM) high angle annular dark field (HAADF) imaging, we probed atomic terminations of S and W to explain observed luminescence enhancement in alternate edges. Faceted void formation in monolayer WS2 was found to be sensitive to annealing temperature, time, gas environment and precursor supply. Our observations of areal coverage evolution over time revealed competition between monolayer WS2 growth and void formation at 850 °C. While the initial stage was dominated by monolayer growth, defect generation and void growth dominated at later stages and provided an optimum processing window for monolayer WS2 as well as faceted void growth. Growth of faceted voids not only followed the geometry of monolayer facets but also showed similar atomic terminations at the edges and thus enabled local manipulation of photoluminescence enhancement with an order of magnitude increase in intensity. The developed CVD processing enabled multi-fold increase in the luminescent active edge length through the formation of faceted voids within the WS2 monolayer.

Phase engineering of seamless heterophase homojunctions with co-existing 3R and 2H phases in WS2 monolayers.

Self-organized semiconductor-semiconductor heterostructures (3R-2H) that coexist in atomically thin 2D monolayers forming homojunctions are of great importance for next-generation nanoelectronics and optoelectronics applications. Herein, we investigated the defect controlled growth of heterogeneous electronic structure within a single domain of monolayer WS2 to enable in-plane homojunctions consisting of alternate 2H semiconducting and 3R semiconducting phases of WS2. X-ray photoelectron, Raman, and photoluminescence spectroscopy along with fluorescence and Kelvin probe force microscopy imaging confirm the formation of homojunctions, enabling a direct correlation between chemical heterogeneity and electronic heterostructure in the atomically thin WS2 monolayer. Quantitative analysis of phase fractions shows 59% stable 2H phase and 41% metastable 3R phase estimated over WS2 flakes of different sizes. Time-resolved fluorescence lifetime imaging confirms distinct contrast between 2H and 3R phases with two distinct lifetimes of 3.2 ns and 1.1 ns, respectively. Kelvin probe force microscopy imaging revealed an abrupt change in the contact potential difference with a depletion width of ∼2.5 µm, capturing a difference in work function of ∼40 meV across the homojunction. Further, the thermal stability of coexisting phases and their temperature dependent optical behavior show a distinct difference among 2H and 3R phases. The investigated aspects of the controlled in plane growth of coexisting phases with seamless homojunctions, their properties, and their thermal stability will enable the development of nanoscale devices that are free from issues of lattice mismatch and grain boundaries.

Real-Time Imaging of Self-Organization and Mechanical Competition in Carbon Nanotube Forest Growth.

The properties of carbon nanotube (CNT) networks and analogous materials comprising filamentary nanostructures are governed by the intrinsic filament properties and their hierarchical organization and interconnection. As a result, direct knowledge of the collective dynamics of CNT synthesis and self-organization is essential to engineering improved CNT materials for applications such as membranes and thermal interfaces. Here, we use real-time environmental transmission electron microscopy (E-TEM) to observe nucleation and self-organization of CNTs into vertically aligned forests. Upon introduction of the carbon source, we observe a large scatter in the onset of nucleation of individual CNTs and the ensuing growth rates. Experiments performed at different temperatures and catalyst particle densities show the critical role of CNT density on the dynamics of self-organization; low-density CNT nucleation results in the CNTs becoming pinned to the substrate and forming random networks, whereas higher density CNT nucleation results in self-organization of the CNTs into bundles that are oriented perpendicular to the substrate. We also find that mechanical coupling between growing CNTs alters their growth trajectory and shape, causing significant deformations, buckling, and defects in the CNT walls. Therefore, it appears that CNT-CNT coupling not only is critical for self-organization but also directly influences CNT quality and likely the resulting properties of the forest. Our findings show that control of the time-distributed kinetics of CNT nucleation and bundle formation are critical to manufacturing well-organized CNT assemblies and that E-TEM can be a powerful tool to investigate the mesoscale dynamics of CNT networks.