Polymorphism-driven Distinct Nanomechanical, Optical, Photophysical, and Conducting Properties in a Benzothiophene-quinoline.

Polymorphic forms of organic conjugated small molecules, with their unique molecular shapes, packing arrangements, and interaction patterns, provide an excellent opportunity to uncover how their microstructures influence their observable properties. Ethyl-2-(1-benzothiophene-2-yl)quinoline-4-carboxylate (BZQ) exists as dimorphs with distinct crystal habits - blocks (BZB) and needles (BZN). The crystal forms differ in their molecular arrangements - BZB has a slip-stacked column-like structure in contrast to a zig-zag crystal packing with limited π-overlap in BZN. The BZB crystals characterized by extended π-stacking along [100] demonstrated semiconductor behavior, whereas the BZN, with its zig-zag crystal packing and limited stacking characteristics, was reckoned as an insulator. Monotropically related crystal forms also differ in their nanomechanical properties, with BZB crystals being considerably softer than BZN crystals. This discrepancy in mechanical behavior can be attributed to the distinct molecular arrangements adopted by each crystal form, resulting in unique mechanisms to relieve the strain generated during nanoindentation experiments. Waveguiding experiments on the acicular crystals of BZN revealed the passive waveguiding properties. Excitation of these crystals using a 532 nm laser confirmed the propagation of elastically scattered photons (green) and the subsequent generation of inelastically scattered (orange) photons by the crystals. Further, the dimorphs display dissimilar photoluminescence properties; they are both blue-emissive, but BZN displays twice the quantum yield of BZB. The study underscores the integral role of polymorphism in modulating the mechanical, photophysical, and conducting properties of functional molecular materials. Importantly, our findings reveal the existence of light-emitting crystal polymorphs with varying electric conductivity, a relatively scarce phenomenon in the literature.

Acoustically Induced Giant Synthetic Hall Voltages in Graphene.

Any departure from graphene's flatness leads to the emergence of artificial gauge fields that act on the motion of the Dirac fermions through an associated pseudomagnetic field. Here, we demonstrate the tunability of strong gauge fields in nonlocal experiments using a large planar graphene sheet that conforms to the deformation of a piezoelectric layer by a surface acoustic wave. The acoustic wave induces a longitudinal and a giant synthetic Hall voltage in the absence of external magnetic fields. The superposition of a synthetic Hall potential and a conventional Hall voltage can annihilate the sample's transverse potential at large external magnetic fields. Surface acoustic waves thus provide a promising and facile avenue for the exploitation of gauge fields in large planar graphene systems.

Electrocatalysis on Edge-Rich Spiral WS2 for Hydrogen Evolution.

Transition metal dichalcogenides (TMDs) exhibit promising catalytic properties for hydrogen generation, and several approaches including defect engineering have been shown to increase the active catalytic sites. Despite preliminary understandings in defect engineering, insights on the role of various types of defects in TMDs for hydrogen evolution catalysis are limited. Screw dislocation-driven (SDD) growth is a line defect and yields fascinating spiral and pyramidal morphologies for TMDs with a large number of edge sites, resulting in very interesting electronic and catalytic properties. The role of dislocation lines and edge sites of these spiral structures on their hydrogen evolution catalytic properties is unexplored. Here we show that the large number of active edge sites connected together by dislocation lines in the vertical direction for a spiral WS2 domain results in exceptional catalytic properties toward hydrogen evolution reaction. A micro-electrochemical cell fabricated by photo- and electron beam-lithography processes is used to study the electrocatalytic activity of a single spiral WS2 domain, controllably grown by chemical vapor deposition. Conductive atomic force microscopy studies show improved vertical conduction for the spiral domain, which is compared with monolayer and mechanically exfoliated thick WS2 flakes. The obtained results are interesting and shed light on the role of SDD line defects, which contribute to large number of edge sites without compromising the vertical electrical conduction, on the electrocatalytic properties of TMDs for hydrogen evolution.

Stable and scalable 1T MoS2 with low temperature-coefficient of resistance.

Monolithic realization of metallic 1T and semiconducting 2H phases makes MoS2 a potential candidate for future microelectronic circuits. A method for engineering a stable 1T phase from the 2H phase in a scalable manner and an in-depth electrical characterization of the 1T phase is wanting at large. Here we demonstrate a controllable and scalable 2H to 1T phase engineering technique for MoS2 using microwave plasma. Our method allows lithographically defining 1T regions on a 2H sample. The 1T samples show excellent temporal and thermal stability making it suitable for standard device fabrication techniques. We conduct both two-probe and four-probe electrical transport measurements on devices with back-gated field effect transistor geometry in a temperature range of 4 K to 300 K. The 1T samples exhibit Ohmic current-voltage characteristics in all temperature ranges without any dependence to the gate voltage, a signature of a metallic state. The sheet resistance of our 1T MoS2 sample is considerably lower and the carrier concentration is a few orders of magnitude higher than that of the 2H samples. In addition, our samples show negligible temperature dependence of resistance from 4 K to 300 K ruling out any hoping mediated or activated electrical transport.

Split-gated point-contact for electrostatic confinement of transport in MoS2/h-BN hybrid structures.

Electrostatically defined nanoscale devices on two-dimensional semiconductor heterostructures are the building blocks of various quantum electrical circuits. Owing to its atomically flat interfaces and the inherent two-dimensional nature, van der Waals heterostructures hold the advantage of large-scale uniformity, flexibility and portability over the conventional bulk semiconductor heterostructures. In this letter we show the operation of a split-gate defined point contact device on a MoS2/h-BN heterostructure, the first step towards realizing electrostatically gated quantum circuits on van der Waals semiconductors. By controlling the voltage on the split-gate we are able to control and confine the electron flow in the device leading to the formation of the point contact. The formation of the point contact in our device is elucidated by the three characteristic regimes observed in the pinch-off curve; transport similar to the conventional FET, electrostatically confined transport and the tunneling dominated transport. We explore the role of the carrier concentration and the drain-source voltages on the pinch-off characteristics. We are able to tune the pinch-off characteristics by varying the back-gate voltage at temperatures ranging from 4 K to 300 K.

Topography preserved microwave plasma etching for top-down layer engineering in MoS2 and other van der Waals materials.

A generic and universal layer engineering strategy for van der Waals (vW) materials, scalable and compatible with the current semiconductor technology, is of paramount importance in realizing all-two-dimensional logic circuits and to move beyond the silicon scaling limit. In this letter, we demonstrate a scalable and highly controllable microwave plasma based layer engineering strategy for MoS2 and other vW materials. Using this technique we etch MoS2 flakes layer-by-layer starting from an arbitrary thickness and area down to the mono- or the few-layer limit. From Raman spectroscopy, atomic force microscopy, photoluminescence spectroscopy, scanning electron microscopy and transmission electron microscopy, we confirm that the structural and morphological properties of the material have not been compromised. The process preserves the pre-etch layer topography and yields a smooth and pristine-like surface. We explore the electrical properties utilising a field effect transistor geometry and find that the mobility values of our samples are comparable to those of the pristine ones. The layer removal does not involve any reactive gasses or chemical reactions and relies on breaking the weak inter-layer vW interaction making it a generic technique for a wide spectrum of layered materials and heterostructures. We demonstrate the wide applicability of the technique by extending it to other systems such as graphene, h-BN and WSe2. In addition, using microwave plasma in combination with standard lithography, we illustrate a lateral patterning scheme making this process a potential candidate for large scale device fabrication in addition to layer engineering.