Shifts in Valence States in Bimetallic MXenes Revealed by Electron Energy-Loss Spectroscopy (EELS)

MXenes are an emergent class of two-dimensional materials with a very wide spectrum of promising applications. The synthesis of multiple MXenes, specifically solid-solution MXenes, allows fine tuning of their properties, expands their range of applications, and leads to enhanced performance. The functionality of solid-solution MXenes is closely related to the valence state of their constituents: transition metals, oxygen, carbon, and nitrogen. However, the impact of changes in the oxidation state of elements in MXenes is not well understood. In this work, three interrelated solid-solution MXene systems (Ti2-yNbyCTx, Nb2-yVyCTx, and Ti2-yVyCTx) were investigated with scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy (EELS) to determine the localized valence states of metals at the nanoscale. The analysis demonstrates changes in the electronic configuration of V upon modification of the overall composition and within individual MXene flakes. These shifts of oxidation state can explain the nonlinear optical and electronic features of solid-solution MXenes. Vanadium appears to be particularly sensitive to modification of the valence state, while titanium maintains the same oxidation state in Ti-Nb and Ti-V MXenes, regardless of stoichiometry. The study also explains Nb's influential role in the previously observed electronic properties in the Nb-V and Nb-Ti systems.

Raman spectra of twisted bilayer graphene close to the magic angle

In this work, we study the Raman spectra of twisted bilayer graphene samples as a function of their twist-angles (θ), ranging from 0.03º to 3.40º, where local θ are determined by analysis of their associated moiré superlattices, as imaged by scanning microwave impedance microscopy. Three standard excitation laser lines are used (457, 532, and 633 nm wavelengths), and the main Raman active graphene bands (G and 2D) are considered. Our results reveal that electron-phonon interaction influences the G band's linewidth close to the magic angle regardless of laser excitation wavelength. Also, the 2D band lineshape in the θ < 1º regime is dictated by crystal lattice and depends on both the Bernal (AB and BA) stacking bilayer graphene and strain soliton regions (SP) [1]. We propose a geometrical model to explain the 2D lineshape variations, and from it, we estimate the SP width when moving towards the magic angle.

Designing spin-textured flat bands in twisted graphene multilayers via helimagnet encapsulation

Twisted graphene multilayers provide tunable platforms to engineer flat bands and exploit the associated strongly correlated physics. The two-dimensional nature of these systems makes them suitable for encapsulation by materials that break specific symmetries. In this context, recently discovered two-dimensional helimagnets, such as the multiferroic monolayer NiI2, are specially appealing for breaking time-reversal and inversion symmetries due to their nontrivial spin textures. Here we show that this spin texture can be imprinted on the electronic structure of twisted bilayer graphene by proximity effect. We discuss the dependence of the imprinted spin texture on the wave-vector of the helical structure, and on the strength of the effective local exchange field. Based on these results we discuss the nature of the superconducting instabilities that can take place in helimagnet encapsulated twisted bilayer graphene. Our results put forward helimagnetic encapsulation as a powerful way of designing spin-textured flat band systems, providing a starting point to engineer a new family of correlated moire states.

Spatial variation of geometry, binding, and electronic properties in the moiré superstructure of MoS2 on Au(111)

The lattice mismatch between a monolayer of MoS2 and its Au(111) substrate induces a moiré superstructure. The local variation of the registry between sulfur and gold atoms at the interface leads to a periodic pattern of strongly and weakly interacting regions. In consequence, also the electronic bands show a spatial variation. We use scanning tunneling microscopy and spectroscopy (STM/STS), x-ray photoelectron spectroscopy (XPS) and x-ray standing wave (XSW) for a determination of the geometric and electronic structure. The experimental results are corroborated by density functional theory (DFT). We obtain the geometric structure of the supercell with high precision, identify the fraction of interfacial atoms that are strongly interacting with the substrate, and analyze the variation of the electronic structure in dependence of the location within the moiré unit cell and the nature of the band.

Floquet band engineering and topological phase transitions in 1T’ transition metal dichalcogenides

Using ab initio tight-binding approaches, we investigate Floquet band engineering of the 1T’ phase of transition metal dichalcogenides (MX2, M = W, Mo and X = Te, Se, S) monolayers under the irradiation with circularly polarized light. Our first principles calculations demonstrate that light can induce important transitions in the topological phases of this emerging materials family. For example, upon irradiation, Te-based MX2 undergoes a phase transition from quantum spin Hall (QSH) semimetal to time-reversal symmetry broken QSH insulator with a nontrivial band gap of up to 92.5 meV. On the other hand, Se- and S-based MX2 undergoes the topological phase transition from the QSH effect to the quantum anomalous Hall (QAH) effect and into trivial phases with increasing light intensity. From a general perspective, our work brings further insight into non-equilibrium topological systems.

Friction anisotropy of violet phosphorene and its surface structure direction identification

Violet phosphorene, a recently determined semiconducting two-dimensional elemental structure, is a promising electronic and optoelectronic material. The nano-tribological properties of violet phosphorene nanoflakes are essential for their micro device applications. A friction anisotropy has been demonstrated for the violet phosphorene nanoflakes by lateral force microscope due to the sub-nanorod components of violet phosphorus. The friction forces of the violet phosphorene nanoflakes have been demonstrated to be valley along sub-nano rod direction and peak across the sub-nanorod direction with a period of 180°, resulting in a fast identification of the surface structure direction of violet phosphorene. The friction of violet phosphorene nanoflakes has also been shown to increase with increasing scanning pressure. However, it is not sensitive to scanning speed or layers. The friction of the violet phosphorene nanoflakes have also been demonstrated to increase when exposure to air for hours. The friction and adhesion features of violet phosphorene nanoflakes provide valuable foundation for violet phosphorene based devices.

Direct Measurement of Biexcitons in Monolayer WS2

The optical properties of atomically thin transition metal dichalcogenides (TMDCs) are dominated by Coulomb bound quasi-particles, such as excitons, trions, and biexcitons. Due to the number and density of possible states, attributing different spectral peaks to the specific origin can be difficult. In particular, there has been much conjecture around the presence, binding energy and/or nature of biexcitons in these materials. In this work, we remove any ambiguity in identifying and separating the optically excited biexciton in monolayer WS2 using two-quantum multidimensional coherent spectroscopy (2Q-MDCS), a technique that directly and selectively probes doubly-excited states, such as biexcitons. The energy difference between the unbound two-exciton state and the biexciton is the fundamental definition of biexciton binding energy and is measured to be 26 ± 2 meV. Furthermore, resolving the biexciton peaks in 2Q-MDCS allows us to identify that the biexciton observed here is composed of two bright excitons in opposite valleys.

Surface and dynamical properties of GeI2

GeI2 is an interesting two-dimensional (2D) wide-band gap semiconductor because of diminished edge scattering due to an absence of dangling bonds. Angle-resolved x-ray photoemission spectroscopy (ARXPS) indicates a germanium rich surface, and a surface to bulk core-level shift of 1.8 eV in binding energy, between the surface and bulk components of the Ge 2p3/2 core-level, making clear that the surface is different from the bulk. Temperature dependent studies indicate an effective Debye temperature (θD ) of 186 ± 18 K for the germanium x-ray photoemission spectroscopy (XPS) feature associated with the surface. These measurements also suggest an unusually high effective Debye temperature for iodine (587 ± 31 K), implying that iodine is present in the bulk of the material, and not the surface. From optical absorbance, GeI2 is seen to have an indirect (direct) optical band gap of 2.60 (2.8) ± 0.02 (0.1) eV, consistent with the expectations. Temperature dependent magnetometry indicates that GeI2 is moment paramagnetic at low temperatures (close to 4 K) and shows a diminishing saturation moment at high temperatures (close to 300 K and above).

Chemical etching manipulated local electronic structure upheaval of graphdiyne for efficient hydrogen evolution

Graphdiyne (GDY), featured with unique sp2, sp-hybridized form and inherent inhomogeneous electron distribution, retains great expectation to be developed into highly efficient electrocatalysts for hydrogen evolution reaction (HER). However, the state-of-the-art GDY-based electrocatalysts still suffer from weak catalytic activity and sluggish reaction kinetics originating from the severe scarcity of in-plane active sites and insufficient electrical conductivity. Targeted at this bottleneck issue, electronic structure regulation, recognized as an extremely precise technical route, is promising to improve HER performances of carbon-based electrocatalysts. Herein, a facile controllable chemical etching strategy is well leveraged to introduce sp2-hybridized carbon-oxygen bonds (Csp2-O) into GDY for precise manipulation both of its electronic and spatial structures. Experimental results and theoretical calculations coherently manifest that Csp2-O introduction into GDY can not only induce its electronic structure upheaval to strengthen surface electron transport capability, but also trigger intensive carbon-oxygen p-p orbital hybridization to enhance the catalytic activity of acetylenic bond sites. As a result, the optimal GDY sample after etching delivers excellent HER performance with an overpotential of only 101 mV at a current density of 10 mA cm-2 and a low Tafel slope of 54 mV dec-1, which surpasses most of reported metal-free based electrocatalysts. This work provides a universal route for precise modulation of inherent electronic structure in GDY, and can be further extended to boost the overall performances of other carbon-based catalysts

Design of a graphene oxide-BODIPY conjugate for glutathione depletion and photodynamic therapy

Boron dipyrromethene derivates (BODIPYs) are promising photosensitisers (PSs) for cancer treatment using photodynamic therapy (PDT). This study investigates the functionalisation of graphene oxide (GO) with a BODIPY derivate for glutathione (GSH) depletion and PDT. The functionalisation of GO with a 3,5-dichloro-8-(4-boronophenyl) BODIPY via a diol derivatisation with the phenyl boronic acid moiety at the meso position of the BODIPY core, allowed to preserve the intrinsic properties of GO. We demonstrated that both chlorine atoms were substituted by GSH in the presence of glutathione transferase (GST), inducing a relevant bathochromic shift in the absorption/emission features and thus generating the active PS. Ex vitro assessment using cell lysates containing cytoplasmatic GST revealed the intracellular catalytic mechanism for the nucleophilic substitution of the GO-BODIPY adduct with GSH. Confocal microscopy studies showed important differences in the cellular uptake of free BODIPY and GO-BODIPY and revealed the coexistence of GO-BODIPY, GO-BODIPY-GS, and GO-BODIPY-GS2 species inside vesicles and in the cytoplasm of the cells after 24 h of incubation. In vitro biocompatibility and safety of GO and GO-BODIPY were evaluated in 2D and 3D models of prostate adenocarcinoma cells (PC-3), where no toxicity was observed up to 100 µg/mL of GO/GO-BODIPY in all treated groups 24 h post-treatment (cell viability > 90%). Only a slight decrease to 80% at 100 µg/mL was observed after 48 h of incubation. We demonstrated the efficacy of a GO adduct containing an α-chlorine-substituted BODIPY for the simultaneous depletion of intracellular GSH and the photogeneration of reactive oxygen species using a halogen white light source (5.4 mW/cm2) with a maximum in the range of 500-800 nm, which significantly reduced cell viability (< 50%) after irradiation. Our study provides a new vision on how to apply BODIPY derivates and potentiate the toxicity of PDT in prostate and other types of cancer.