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1.
Proc Natl Acad Sci U S A ; 121(28): e2400084121, 2024 Jul 09.
Article in English | MEDLINE | ID: mdl-38968114

ABSTRACT

MXenes have demonstrated potential for various applications owing to their tunable surface chemistry and metallic conductivity. However, high temperatures can accelerate MXene film oxidation in air. Understanding the mechanisms of MXene oxidation at elevated temperatures, which is still limited, is critical in improving their thermal stability for high-temperature applications. Here, we demonstrate that Ti[Formula: see text]C[Formula: see text]T[Formula: see text] MXene monoflakes have exceptional thermal stability at temperatures up to 600[Formula: see text]C in air, while multiflakes readily oxidize in air at 300[Formula: see text]C. Density functional theory calculations indicate that confined water between Ti[Formula: see text]C[Formula: see text]T[Formula: see text] flakes has higher removal energy than surface water and can thus persist to higher temperatures, leading to oxidation. We demonstrate that the amount of confined water correlates with the degree of oxidation in stacked flakes. Confined water can be fully removed by vacuum annealing Ti[Formula: see text]C[Formula: see text]T[Formula: see text] films at 600[Formula: see text]C, resulting in substantial stability improvement in multiflake films (can withstand 600[Formula: see text]C in air). These findings provide fundamental insights into the kinetics of confined water and its role in Ti[Formula: see text]C[Formula: see text]T[Formula: see text] oxidation. This work enables the use of stable monoflake MXenes in high-temperature applications and provides guidelines for proper vacuum annealing of multiflake films to enhance their stability.

2.
Nano Lett ; 24(18): 5436-5443, 2024 May 08.
Article in English | MEDLINE | ID: mdl-38656103

ABSTRACT

The ultrahigh surface area of two-dimensional materials can drive multimodal coupling between optical, electrical, and mechanical properties that leads to emergent dynamical responses not possible in three-dimensional systems. We observed that optical excitation of the WS2 monolayer above the exciton energy creates symmetrically patterned mechanical protrusions which can be controlled by laser intensity and wavelength. This observed photostrictive behavior is attributed to lattice expansion due to the formation of polarons, which are charge carriers dressed by lattice vibrations. Scanning Kelvin probe force microscopy measurements and density functional theory calculations reveal unconventional charge transport properties such as the spatially and optical intensity-dependent conversion in the WS2 monolayer from apparent n- to p-type and the subsequent formation of effective p-n junctions at the boundaries between regions with different defect densities. The strong opto-electrical-mechanical coupling in the WS2 monolayer reveals previously unexplored properties, which can lead to new applications in optically driven ultrathin microactuators.

3.
Proc Natl Acad Sci U S A ; 117(44): 27104-27110, 2020 Nov 03.
Article in English | MEDLINE | ID: mdl-33077590

ABSTRACT

We report the optical conductivity in high-quality crystals of the chiral topological semimetal CoSi, which hosts exotic quasiparticles known as multifold fermions. We find that the optical response is separated into several distinct regions as a function of frequency, each dominated by different types of quasiparticles. The low-frequency intraband response is captured by a narrow Drude peak from a high-mobility electron pocket of double Weyl quasiparticles, and the temperature dependence of the spectral weight is consistent with its Fermi velocity. By subtracting the low-frequency sharp Drude and phonon peaks at low temperatures, we reveal two intermediate quasilinear interband contributions separated by a kink at 0.2 eV. Using Wannier tight-binding models based on first-principle calculations, we link the optical conductivity above and below 0.2 eV to interband transitions near the double Weyl fermion and a threefold fermion, respectively. We analyze and determine the chemical potential relative to the energy of the threefold fermion, revealing the importance of transitions between a linearly dispersing band and a flat band. More strikingly, below 0.1 eV our data are best explained if spin-orbit coupling is included, suggesting that at these energies, the optical response is governed by transitions between a previously unobserved fourfold spin-3/2 node and a Weyl node. Our comprehensive combined experimental and theoretical study provides a way to resolve different types of multifold fermions in CoSi at different energy. More broadly, our results provide the necessary basis to interpret the burgeoning set of optical and transport experiments in chiral topological semimetals.

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