Two-dimensional (2D) layered transition metal dichalcogenides (TMDs) have recently attracted tremendous interest as potential valleytronic and nanoelectronic materials, in addition to being well-known as excellent lubricants in the bulk. The interlayer van der Waals (vdW) coupling and low-frequency phonon modes and how they evolve with the number of layers are important for both the mechanical and the electrical properties of 2D TMDs. Here we uncover the ultralow frequency interlayer breathing and shear modes in few-layer MoS2 and WSe2, prototypical layered TMDs, using both Raman spectroscopy and first principles calculations. Remarkably, the frequencies of these modes can be perfectly described using a simple linear chain model with only nearest-neighbor interactions. We show that the derived in-plane (shear) and out-of-plane (breathing) force constants from experiment remain the same from two-layer 2D crystals to the bulk materials, suggesting that the nanoscale interlayer frictional characteristics of these excellent lubricants should be independent of the number of layers.
Although great progress has been achieved in the study of graphene, the small current ON/OFF ratio in graphene-based field-effect transistors (FETs) limits its application in the fields of conventional transistors or logic circuits for low-power electronic switching. Recently, layered transition metal dichalcogenide (TMD) materials, especially MoS2, have attracted increasing attention. In contrast to its bulk material with an indirect band gap, a single-layer (1L) MoS2 nanosheet is a semiconductor with a direct band gap of ~1.8 eV, which makes it a promising candidate for optoelectronic applications due to the enhancement of photoluminescence and high current ON/OFF ratio. Compared with TMD nanosheets prepared by chemical vapor deposition and liquid exfoliation, mechanically exfoliated ones possess pristine, clean, and high-quality structures, which are suitable for the fundamental study and potential applications based on their intrinsic thickness-dependent properties. In this Account, we summarize our recent research on the preparation, characterization, and applications of 1L and multilayer MoS2 and WSe2 nanosheets produced by mechanical exfoliation. During the preparation of nanosheets, we proposed a simple optical identification method to distinguish 1L and multilayer MoS2 and WSe2 nanosheets on a Si substrate coated with 90 and 300 nm SiO2. In addition, we used Raman spectroscopy to characterize mechanically exfoliated 1L and multilayer WSe2 nanosheets. For the first time, a new Raman peak at 308 cm(-1) was observed in the spectra of WSe2 nanosheets except for the 1L WSe2 nanosheet. Importantly, we found that the 1L WSe2 nanosheet is very sensitive to the laser power during characterization. The high power laser-induced local oxidation of WSe2 nanosheets and single crystals was monitored by Raman spectroscopy and atomic force microscopy (AFM). Hexagonal and monoclinic structured WO3 thin films were obtained from the local oxidization of single- to triple-layer (1L-3L) and quadruple- to quintuple-layer (4L-5L) WSe2 nanosheets, respectively. Then, we present Raman characterization of shear and breathing modes of 1L and multilayer MoS2 and WSe2 nanosheets in the low frequency range (<50 cm(-1)), which can be used to accurately identify the layer number of nanosheets. Magnetic force microscopy was used to characterize 1L and multilayer MoS2 nanosheets, and thickness-dependent magnetic response was found. In the last part, we briefly introduce the applications of 1L and multilayer MoS2 nanosheets in the fields of gas sensors and phototransistors.
Gold, silver, platinum and palladium typically crystallize with the face-centred cubic structure. Here we report the high-yield solution synthesis of gold nanoribbons in the 4H hexagonal polytype, a previously unreported metastable phase of gold. These gold nanoribbons undergo a phase transition from the original 4H hexagonal to face-centred cubic structure on ligand exchange under ambient conditions. Using monochromated electron energy-loss spectroscopy, the strong infrared plasmon absorption of single 4H gold nanoribbons is observed. Furthermore, the 4H hexagonal phases of silver, palladium and platinum can be readily stabilized through direct epitaxial growth of these metals on the 4H gold nanoribbon surface. Our findings may open up new strategies for the crystal phase-controlled synthesis of advanced noble metal nanomaterials.
The physical and electronic properties of ultrathin two-dimensional (2D) layered nanomaterials are highly related to their thickness. Therefore, the rapid and accurate identification of single- and few- to multilayer nanosheets is essential to their fundamental study and practical applications. Here, a universal optical method has been developed for simple, rapid, and reliable identification of single- to quindecuple-layer (1L-15L) 2D nanosheets, including graphene, MoS2, WSe2, and TaS2, on Si substrates coated with 90 or 300 nm SiO2. The optical contrast differences between the substrates and 2D nanosheets with different layer numbers were collected and tabulated, serving as a standard reference, from which the layer number of a given nanosheet can be readily and reliably determined without using complex calculation or expensive instrument. Our general optical identification method will facilitate the thickness-dependent study of various 2D nanomaterials and expedite their research toward practical applications.
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