Single-atom doping of MoS2 with manganese enables ultrasensitive detection of dopamine: Experimental and computational approach.

Two-dimensional transition metal dichalcogenides (TMDs) emerged as a promising platform to construct sensitive biosensors. We report an ultrasensitive electrochemical dopamine sensor based on manganese-doped MoS2 synthesized via a scalable two-step approach (with Mn ~2.15 atomic %). Selective dopamine detection is achieved with a detection limit of 50 pM in buffer solution, 5 nM in 10% serum, and 50 nM in artificial sweat. Density functional theory calculations and scanning transmission electron microscopy show that two types of Mn defects are dominant: Mn on top of a Mo atom (MntopMo) and Mn substituting a Mo atom (MnMo). At low dopamine concentrations, physisorption on MnMo dominates. At higher concentrations, dopamine chemisorbs on MntopMo, which is consistent with calculations of the dopamine binding energy (2.91 eV for MntopMo versus 0.65 eV for MnMo). Our results demonstrate that metal-doped layered materials, such as TMDs, constitute an emergent platform to construct ultrasensitive and tunable biosensors.

Universal In Situ Substitutional Doping of Transition Metal Dichalcogenides by Liquid-Phase Precursor-Assisted Synthesis.

Doping lies at the heart of modern semiconductor technologies. Therefore, for two-dimensional (2D) semiconducting transition metal dichalcogenides (TMDs), the significance of controlled doping is no exception. Recent studies have indicated that, by substitutionally doping 2D TMDs with a judicious selection of dopants, their electrical, optical, magnetic, and catalytic properties can be effectively tuned, endowing them with great potential for various practical applications. Herein, and inspired by the sol-gel process, we report a liquid-phase precursor-assisted approach for in situ substitutional doping of monolayered TMDs and their in-plane heterostructures with tunable doping concentration. This highly reproducible route is based on the high-temperature chalcogenation of spin-coated aqueous solutions containing host and dopant precursors. The precursors are mixed homogeneously at the atomic level in the liquid phase prior to the synthesis process, thus allowing for an improved doping uniformity and controllability. We further demonstrate the incorporation of various transition metal atoms, such as iron (Fe), rhenium (Re), and vanadium (V), into the lattice of TMD monolayers to form Fe-doped WS2, Re-doped MoS2, and more complex material systems such as V-doped in-plane WxMo1-xS2-MoxW1-xS2 heterostructures, among others. We envisage that our developed approach is universal and could be extended to incorporate a variety of other elements into 2D TMDs and create in-plane heterointerfaces in a single step, which may enable applications such as electronics and spintronics at the 2D limit.

Raman and electrical transport properties of few-layered arsenic-doped black phosphorus.

Black phosphorus (b-P) is an allotrope of phosphorus whose properties have attracted great attention. In contrast to other 2D compounds, or pristine b-P, the properties of b-P alloys have yet to be explored. In this report, we present a detailed study on the Raman spectra and on the temperature dependence of the electrical transport properties of As-doped black phosphorus (b-AsP) for an As fraction x = 0.25. The observed complex Raman spectra were interpreted with the support of Density Functional Theory (DFT) calculations since each original mode splits in three due to P-P, P-As, and As-As bonds. Field-effect transistors (FET) fabricated from few-layered b-AsP exfoliated onto Si/SiO2 substrates exhibit hole-doped like conduction with a room temperature ON/OFF current ratio of ∼103 and an intrinsic field-effect mobility approaching ∼300 cm2 V-1 s-1 at 300 K which increases up to 600 cm2 V-1 s-1 at 100 K when measured via a 4-terminal method. Remarkably, these values are comparable to, or higher, than those initially reported for pristine b-P, indicating that this level of As doping is not detrimental to its transport properties. The ON to OFF current ratio is observed to increase up to 105 at 4 K. At high gate voltages b-AsP displays metallic behavior with the resistivity decreasing with decreasing temperature and saturating below T ∼100 K, indicating a gate-induced insulator to metal transition. Similarly to pristine b-P, its transport properties reveal a high anisotropy between armchair (AC) and zig-zag (ZZ) directions. Electronic band structure computed through periodic dispersion-corrected hybrid Density Functional Theory (DFT) indicate close proximity between the Fermi level and the top of the valence band(s) thus explaining its hole doped character. Our study shows that b-AsP has potential for optoelectronics applications that benefit from its anisotropic character and the ability to tune its band gap as a function of the number of layers and As content.

Excitonic Complexes and Emerging Interlayer Electron-Phonon Coupling in BN Encapsulated Monolayer Semiconductor Alloy: WS0.6Se1.4.

Monolayer transition metal dichalcogenides (TMDs) possess superior optical properties, including the valley degree of freedom that can be accessed through the excitation light of certain helicity. Although WS2 and WSe2 are known for their excellent valley polarization due to the strong spin-orbit coupling, the optical bandgap is limited by the ability to choose from only these two materials. This limitation can be overcome through the monolayer alloy semiconductor, WS2 xSe2(1- x), which promises an atomically thin semiconductor with tunable bandgap. In this work, we show that the high-quality BN encapsulated monolayer WS0.6Se1.4 inherits the superior optical properties of tungsten-based TMDs, including a trion splitting of ∼6 meV and valley polarization as high as ∼60%. In particular, we demonstrate for the first time the emerging and gate-tunable interlayer electron-phonon coupling in the BN/WS0.6Se1.4/BN van der Waals heterostructure, which renders the otherwise optically silent Raman modes visible. In addition, the emerging Raman signals can be drastically enhanced by the resonant coupling to the 2s state of the monolayer WS0.6Se1.4 A exciton. The BN/WS2 xSe2(1- x)/BN van der Waals heterostructure with a tunable bandgap thus provides an exciting platform for exploring the valley degree of freedom and emerging excitonic physics in two-dimension.

Large second harmonic generation in alloyed TMDs and boron nitride nanostructures.

First principles methods are used to explicitly calculate the nonlinear susceptibility (χ(2)(2ω, ω, ω)) representing the second harmonic generation (SHG) of two dimensional semiconducting materials, namely transition metal dichalcogenides (TMDs) and Boron Nitride (BN). It is found that alloying TMDs improves their second harmonic response, with MoTeS alloys exhibiting the highest of all hexagonal alloys at low photon energies. Moreover, careful examination of the relationship between the concentration of Se in MoxSeySz alloys shows that the SHG intensity can be tuned by modifying the stoichiometry. In addition, materials with curvature can have large second harmonic susceptibility. Of all the calculated monolayer structures, the hypothetical TMD Haeckelites NbSSe and Nb0.5Ta0.5S2 exhibit the highest χ(2), while one of the porous 3D structures constructed from 2D hBN exhibits a larger χ(2) than known large band gap 3-D materials.

Traditional Semiconductors in the Two-Dimensional Limit.

Interest in two-dimensional materials has exploded in recent years. Not only are they studied due to their novel electronic properties, such as the emergent Dirac fermion in graphene, but also as a new paradigm in which stacking layers of distinct two-dimensional materials may enable different functionality or devices. Here, through first-principles theory, we reveal a large new class of two-dimensional materials which are derived from traditional III-V, II-VI, and I-VII semiconductors. It is found that in the ultrathin limit the great majority of traditional binary semiconductors studied (a series of 28 semiconductors) are not only kinetically stable in a two-dimensional double layer honeycomb structure, but more energetically stable than the truncated wurtzite or zinc-blende structures associated with three dimensional bulk. These findings both greatly increase the landscape of two-dimensional materials and also demonstrate that in the double layer honeycomb form, even ordinary semiconductors, such as GaAs, can exhibit exotic topological properties.

Resonant Raman and Exciton Coupling in High-Quality Single Crystals of Atomically Thin Molybdenum Diselenide Grown by Vapor-Phase Chalcogenization.

We report a detailed investigation on Raman spectroscopy in vapor-phase chalcogenization grown, high-quality single-crystal atomically thin molybdenum diselenide samples. Measurements were performed in samples with four different incident laser excitation energies ranging from 1.95 eV ⩽ Eex ⩽ 2.71 eV, revealing rich spectral information in samples ranging from N = 1-4 layers and a thick, bulk sample. In addition to previously observed (and identified) peaks, we specifically investigate the origin of a peak near ω ≈ 250 cm-1. Our density functional theory and Bethe-Salpeter calculations suggest that this peak arises from a double-resonant Raman process involving the ZA acoustic phonon perpendicular to the layer. This mode appears prominently in freshly prepared samples and disappears in aged samples, thereby offering a method for ascertaining the high optoelectronic quality of freshly prepared 2D-MoSe2 crystals. We further present an in-depth investigation of the energy-dependent variation of the position of this and other peaks and provide evidence of C-exciton-phonon coupling in monolayer MoSe2. Finally, we show how the signature peak positions and intensities vary as a function of layer thickness in these samples.