Sulfur Vacancy Related Optical Transitions in Graded Alloys of MoxW1-xS2 Monolayers

Engineering the electronic bandgap is of utmost importance in diverse domains ranging from information processing and communication technology to sensing and renewable energy applications. Transition metal dichalcogenides (TMDCs) provide an ideal platform for achieving this goal through techniques including alloying, doping, and creating in-plane or out-of-plane heterostructures. Here, we report on the synthesis and characterization of atomically controlled two-dimensional graded alloy of MoxW1-xS2, wherein the center region is Mo rich and gradually transitions towards a higher concentration of W atoms at the edges. This unique alloy structure leads to a continuously tunable bandgap, ranging from 1.85 eV in the center to 1.95 eV at the edges consistent with the larger band gap of WS2 relative to MoS2. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy showed the presence of sulfur monovacancy, VS, whose concentration varied across the graded MoxW1-xS2 layer as a function of Mo content with the highest value in the Mo rich center region. Optical spectroscopy measurements supported by ab initio calculations reveal a doublet electronic state of VS, which was split due to the spin-orbit interaction, with energy levels close to the conduction band or deep in the band gap depending on whether the vacancy is surrounded by W atoms or Mo atoms. This unique electronic configuration of VS in the alloy gave rise to four spin-allowed optical transitions between the VS levels and the valence bands. Our work highlights the potential of simultaneous defect and optical engineering of novel devices based on these 2D monolayers.Comment: 65 pages, 7 figures in main text. 21 figures in supplemental dat

Quantitative Nanoscale Absorption Mapping: A Novel Technique To Probe Optical Absorption of Two-Dimensional Materials

Two-dimensional semiconductors, in particular transition metal dichalcogenides and related heterostructures, have gained increasing interest as they constitute potential new building blocks for the next generation of electronic and optoelectronic applications. In this work, we develop a novel nondestructive and noncontact technique for mapping the absorption properties of 2D materials, by taking advantage of the underlying substrate cathodoluminescence emission. We map the quantitative absorption of MoS2 and MoSe2 monolayers, obtained on sapphire and oxidized silicon, with nanoscale resolution. We extend our technique to the characterization of the absorption properties of MoS2/MoSe2 van der Waals heterostructures. We demonstrate that interlayer excitonic phenomena enhance the absorption in the UV range. Our technique also highlights the presence of defects such as grain boundaries and ad-layers. We provide measurements on the absorption of grain boundaries in monolayer MoS2 at different merging angles. We observe a higher absorption yield of randomly oriented monolayers with respect to 60° rotated monolayers. This work opens up a new possibility for characterizing the functional properties two dimensional semiconductors at the nanoscale

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Damage Resistance of a Thermal Barrier Coated Superalloy Used in Aero Turbine Blade under Accelerated Creep Condition

This paper highlights the hot tensile and accelerated creep properties of a thermal barrier coated (TBC) AE 437A alloy used as a candidate blade material in aero engines. Acoustic emission technique has been utilised to characterise the ductile-brittle transition temperature of the bond coat. Results revealed that the DBTT (ductile to brittle transition temperature) of this bond coat is around 923 K, which is in close proximity to the value reported for NiCoCrAlY type of bond coat. Finite element technique used for analysing the equivalent stresses in the bond coat well within the elastic limit, revealed highest order of equivalent stress at 1073 K as the bond coat is ductile above 923 K. The lifetime of the TBC coated superalloy was Superior to that of the bare substrate and that oxidation is likely the cause of the reduced life of the bare substrate as compared to the coated substrate while stress rupture or accelerated creep experiments are carried out in an oxidizing environment.. Delamination of the bond coat and that of the TBC at high stresses during accelerated creep was evident. During accelerated creep, the mode of fracture in the substrate at very high stresses was transgranular whereas that at low stresses was intergranular

Multifunctional Applications Enabled by Fluorination of Hexagonal Boron Nitride

Publication status: PublishedFunder: Shared Equipment AuthorityFunder: Electron Microscopy CenterFunder: Rice University; doi: http://dx.doi.org/10.13039/100007863Funder: Vanier Canada Graduate ScholarshipFunder: Natural Sciences and Engineering Research Council of Canada; doi: http://dx.doi.org/10.13039/501100000038Abstract2D materials exhibit exceptional properties as compared to their macroscopic counterparts, with promising applications in nearly every area of science and technology. To unlock further functionality, the chemical functionalization of 2D structures is a powerful technique that enables tunability and new properties within these materials. Here, the successful effort to chemically functionalize hexagonal boron nitride (hBN), a chemically inert 2D ceramic with weak interlayer forces, using a gas‐phase fluorination process is exploited. The fluorine functionalization guides interlayer expansion and increased polar surface charges on the hBN sheets resulting in a number of vastly improved applications. Specifically, the F‐hBN exhibits enhanced dispersibility and thermal conductivity at higher temperatures by more than 75% offering exceptional performance as a thermofluid additive. Dispersion of low volumes of F‐hBN in lubricating oils also offers marked improvements in lubrication and wear resistance for steel tribological contacts decreasing friction by 31% and wear by 71%. Additionally, incorporating numerous negatively charged fluorine atoms on hBN induces a permanent dipole moment, demonstrating its applicability in microelectronic device applications. The findings suggest that anchoring chemical functionalities to hBN moieties improves a variety of properties for h‐BN, making it suitable for numerous other applications such as fillers or reinforcement agents and developing high‐performance composite structures.</jats:p