Arylazo-3,5-diphenylpyrazole Derivatives: Molecular Probes Exhibiting Reversible Light-induced Phase Transitions for Energy Storage and Direct Photolithographic Patterning.

We report azopyrazole photoswitches decorated with variable N-alkyl and alkoxy chains (for hydrophobic interactions) and phenyl substituents on the pyrazoles (enabling π-π stacking), showing efficient bidirectional photoswitching and reversible light-induced phase transition (LIPT). Extensive spectroscopic, microscopic, and diffraction studies and computations confirmed the manifestation of molecular-level interactions and photoisomerization into macroscopic changes leading to the LIPT phenomena. Using differential scanning calorimetric (DSC) studies, the energetics associated with those accompanying processes were estimated. The long half-lives of Z isomers, high energy contents for isomerization and phase transitions, and the stability of phases over an extended temperature range (-60 to 80 oC) make them excellent candidates for energy storage and release applications. Remarkably, the difference in the solubility of the distinct phases in one of the derivatives allowed us to utilize it as a photoresist in photolithography applications on diverse substrates.

Engineering Catalytically Active Sites by Sculpting Artificial Edges on MoS2 Basal Plane for Dinitrogen Reduction at a Low Overpotential.

Engineering catalytically active sites have been a challenge so far and often relies on optimization of synthesis routes, which can at most provide quantitative enhancement of active facets, however, cannot provide control over choosing orientation, geometry and spatial distribution of the active sites. Artificially sculpting catalytically active sites via laser-etching technique can provide a new prospect in this field and offer a new species of nanocatalyst for achieving superior selectivity and attaining maximum yield via absolute control over defining their location and geometry of every active site at a nanoscale precision. In this work, a controlled protocol of artificial surface engineering is shown by focused laser irradiation on pristine MoS2 flakes, which are confirmed as catalytic sites by electrodeposition of AuNPs. The preferential Au deposited catalytic sites are found to be electrochemically active for nitrogen adsorption and its subsequent reduction due to the S-vacancies rather than Mo-vacancy, as advocated by DFT analysis. The catalytic performance of Au-NR/MoS2 shows a high yield rate of ammonia (11.43 × 10-8  mol s-1 cm-2 ) at a potential as low as -0.1 V versus RHE and a notable Faradaic efficiency of 13.79% during the electrochemical nitrogen reduction in 0.1 m HCl.

Reversible Pressure-Induced Partial Phase Transition in Few-Layer Black Phosphorus.

The experimental identification of structural transitions in layered black phosphorus (BP) under mechanical stress is essential to extend its application in microelectromechanical (MEMS) devices under harsh conditions. High-pressure Raman spectroscopic analysis of BP flakes suggests a transition pressure at ∼4.2 GPa, where the BP's crystal structure progressively transforms from an orthorhombic to a rhombohedral symmetry (blue phosphorus, bP). The phase transition has been identified by observing a transition from blueshift to redshift of the in-plane characteristic Raman modes (B2g and Ag2) with increasing pressure. Recovery of the vibrational frequencies for all three characteristic Raman modes confirms the reversibility of the structural phase transition. First-principles calculations provide insight into the behavior of the Raman modes of BP under high pressure and reveal the mechanism responsible for the partial phase transition from BP to bP, corresponding to a metastable equilibrium state where both phases coexist.

Modulating capacitive response of MoS2 flake by controlled nanostructuring through focused laser irradiation.

Unlike graphene nanostructures, various physical properties of nanostructured MoS2 have remained unexplored due to the lack of established fabrication routes. Herein, we have reported unique electrostatic properties of MoS2 nanostructures, fabricated in a controlled manner of different geometries on 2D flake by using focused laser irradiation technique. Electrostatic force microscopy has been carried out on MoS2 nanostructures by varying tip bias voltage and lift height. The analysis depicts no contrast flip in phase image of the patterned nanostructure due to the absence of free surface charges. However, prominent change in phase shift at the patterned area is observed. Such contrast changes signify the capacitive interaction between tip and nanostructures at varying tip bias voltage and lift height, irrespective of their shape and size. Such unperturbed capacitive behavior of the MoS2 nanostructures offer modulation of capacitance in periodic array on 2D MoS2 flake for potential application in capacitive devices.

Green-Lighting the Sub-Band Gap Excitation in Two-Dimensional Zinc Oxide.

Solar spectrum and sensitivity of human eyes peak at green wavelength range of visible light, and the materials that can respond to a larger part of the visible spectrum are highly sought after. Two-dimensional graphene-like zinc oxide (gZnO) is a wide band gap semiconductor, but photogeneration of electron-hole pairs in it at visible wavelengths has not been achieved so far. Here, the sub-band gap excitation in 2D zinc oxide layers covered with gold nanoparticles is reported. The sub-band gap excitation and corresponding emission are correlated with oxygen interstitials introduced by AuNP deposition in the gZnO lattice. Attachment of AuNPs on gZnO also leads to increased electron availability at oxygen sites of the gZnO lattice, which translates into greater electron availability for sub-band gap excitation. The plasmonically enhanced trap level to conduction band transition constitutes sub-band gap excitation and manifests itself in local surface potential measurements carried out using a Kelvin probe force microscope.

Enhancement of field emission characteristics of carbon nanotubes on oxidation.

Vertically aligned multi-walled carbon nanotubes (CNTs) were grown on p-type silicon wafer using thermal chemical vapor deposition process and subsequently treated with oxygen plasma for oxidation. It was observed that the electron field emission (EFE) characteristics are enhanced. It showed that the turn-on electric field (E(TOE)) of CNTs decreased from 0.67 (untreated) to 0.26 V/microm (oxygen treated). Raman spectra showed that the numbers of defects are increased, which are generated by oxygen-treatment, and absorbed molecules on the CNTs are responsible for the enhancement of EFE. Scanning electron microscopy and Transmission electron microscopy images were used to identify the quality and physical changes of the nanotube morphology and surfaces; revealing the evidence of enhancement in the field emission properties after oxygen-plasma treatment.

Sculpting Artificial Edges in Monolayer MoS2 for Controlled Formation of Surface-Enhanced Raman Hotspots.

Hotspot engineering has the potential to transform the field of surface-enhanced Raman spectroscopy (SERS) by enabling ultrasensitive and reproducible detection of analytes. However, the ability to controllably generate SERS hotspots, with desired location and geometry, over large-area substrates, has remained elusive. In this study, we sculpt artificial edges in monolayer molybdenum disulfide (MoS2) by low-power focused laser-cutting. We find that when gold nanoparticles (AuNPs) are deposited on MoS2 by drop-casting, the AuNPs tend to accumulate predominantly along the artificial edges. First-principles density functional theory (DFT) calculations indicate strong binding of AuNPs with the artificial edges due to dangling bonds that are ubiquitous on the unpassivated (laser-cut) edges. The dense accumulation of AuNPs along the artificial edges intensifies plasmonic effects in these regions, creating hotspots exclusively along the artificial edges. DFT further indicates that adsorption of AuNPs along the artificial edges prompts a transition from semiconducting to metallic behavior, which can further intensify the plasmonic effect along the artificial edges. These effects are observed exclusively for the sculpted (i.e., cut) edges and not observed for the MoS2 surface (away from the cut edges) or along the natural (passivated) edges of the MoS2 sheet. To demonstrate the practical utility of this concept, we use our substrate to detect Rhodamine B (RhB) with a large SERS enhancement (∼104) at the hotspots for RhB concentrations as low as ∼10-10 M. The single-step laser-etching process reported here can be used to controllably generate arrays of SERS hotspots. As such, this concept offers several advantages over previously reported SERS substrates that rely on electrochemical deposition, e-beam lithography, nanoimprinting, or photolithography. Whereas we have focused our study on MoS2, this concept could, in principle, be extended to a variety of 2D material platforms.

Controlled nanofabrication of metal-free SERS substrate on few layered black phosphorus by low power focused laser irradiation.

Black Phosphorous (BP) has intrinsic in-plane ferroelectric properties that may have the inherent capability of SERS response and can be considered as a replacement of metal nanoparticle-based SERS substrates. A simple one-step process has been demonstrated for the controlled nano-structuring and rapid prototyping on a BP flake to develop a metal-free SERS substrate by low power focused laser irradiation. The effect of focused laser irradiation on the surface morphology of the pristine BP flakes has been thoroughly investigated by real time Raman spectroscopy measurements and corresponding AFM height profiling, which confirms that the proposed laser irradiation technique has more advantages over the conventional lithography and is free from undesired contamination. For a 532 nm laser line, the minimum laser power needed to create a nano-void on the BP flake is 25 mW (Power density = ∼15.62 × 105 W cm-2) with 5 s exposure time, where the etching rate is controlled by the laser power and exposure time. By analyzing the geometrical shape of the nano-void created due to laser irradiation, it is possible to identify the armchair and zigzag directions of the BP flake. The experimental results revealed that by controlling the exposure time and laser power, it was possible to perform layer by layer thinning of BP flakes. The proposed thinning process of the BP flake did not alter the pristine quality and no signature of oxidation was found in the Raman spectra, which signified the reliability of this low power laser irradiation technique towards the future nano-fabrication of BP-based devices. The controlled formation of the nano-void array on a few layered BP flake enhanced the local electric field (hot spots) in the vicinity of the nano-voids, resulting in ∼30% Raman intensity enhancement. Such nano-void induced hotspots on the BP flake open up a new species of metal-free SERS substrate, demonstrating pronounced enhancement in the Raman signal of Rhodamine B as high as ∼106 and a limit of detection (LOD) up to ∼10 nM.

Ultrafast Carrier Dynamics of the Exciton and Trion in MoS2 Monolayers Followed by Dissociation Dynamics in Au@MoS2 2D Heterointerfaces.

Many-body states like excitons, biexcitons, and trions play an important role in optoelectronic and photovoltaic applications in 2D materials. Herein, we studied carrier dynamics of excitons and trions in monolayer MoS2 deposited on a SiO2/Si substrate, before and after Au NP deposition, using femtosecond transient absorption spectroscopy. Luminescence measurements confirm the presence of both an exciton and trion in MoS2, which are drastically quenched after deposition of Au NPs, indicating electron transfer from photoexcited MoS2 to Au. Ultrafast study reveals that photogenerated free carriers form excitons with a time scale of ∼500 fs and eventually turn into trions within ∼1.2 ps. Dissociation of excitons and trions has been observed in the presence of Au, with time scales of ∼600 fs and ∼3.7 ps, respectively. Understanding the formation and dissociation dynamics of the exciton and trion in monolayer MoS2 is going to help immensely to design and develop many new 2D devices.

Healing of broken multiwalled carbon nanotubes using very low energy electrons in SEM: a route toward complete recovery.

We report the healing of electrically broken multiwalled carbon nanotubes (MWNTs) using very low energy electrons (3-10 keV) in scanning electron microscopy (SEM). Current-induced breakdown caused by Joule heating has been achieved by applying suitably high voltages. The broken tubes were examined and exposed to electrons of 3-10 keV in situ in SEM with careful maneuvering of the electron beam at the broken site, which results in the mechanical joining of the tube. Electrical recovery of the same tube has been confirmed by performing the current-voltage measurements after joining. This easy approach is directly applicable for the repairing of carbon nanotubes incorporated in ready devices, such as in on-chip horizontal interconnects or on-tip probing applications, such as in scanning tunneling microscopy.

Dramatic enhancement of the emission current density from carbon nanotube based nanosize tips with extremely low onset fields.

Nanostructures based on multiwalled carbon nanotubes (MWNTs) are fabricated using plasma of the mixture of hydrogen and nitrogen gases. The plasma-sharpened tips of nanotubes contain only a few tubes at the apex of the structure and lead to the dramatic enhancement in the emission current density by a factor >10(6) with the onset field as low as 0.16 V/microm. We propose that the nature of the tunneling barrier changes significantly for a nanosize tip at very high local electric field and may lead to the saturation in the emission current density.