Preparation and applications of mechanically exfoliated single-layer and multilayer MoS2 and WSe2 nanosheets.

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.

Graphene oxide architectures prepared by molecular combing on hydrophilic-hydrophobic micropatterns.

A novel graphene oxide (GO) architecture is fabricated on hydrophilic-hydrophobic patterned alkanethiol self-assembled monolayers on Au by molecular combing of GO sheets. With hydrazine reduction, the reduced GO architecture-based device is demonstrated to detect NO2 gas. This simple method shows the potential to control the shape, orientation and position of GO sheets over large areas.

Interlayer breathing and shear modes in few-trilayer MoS2 and WSe2.

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.

Preparation of MoS2-MoO3 hybrid nanomaterials for light-emitting diodes.

A facile strategy to prepare MoS2 -MoO3 hybrid nanomaterials is developed, based on the heat-assisted partial oxidation of lithium-exfoliated MoS2  nanosheets in air followed by thermal-annealing-driven crystallization. The obtained MoS2 -MoO3 hybrid nanomaterial exhibits p-type conductivity. As a proof-of-concept application, an n-type SiC/p-type MoS2 -MoO3 heterojunction is used as the active layer for light-emitting diodes. The origins of the electroluminescence from the device are theoretically investigated. This facile synthesis and application of hybrid nanomaterials opens up avenues to develop new advanced materials for various functional applications, such as in electrics, optoelectronics, clean energy, and information storage.

Graphene oxide scrolls on hydrophobic substrates fabricated by molecular combing and their application in gas sensing.

Well-aligned graphene oxide (GO) scrolls are prepared through the controlled folding/scrolling of single-layer GO sheets using molecular combing on hydrophobic substrates, such as aged gold substrate, polydimethylsiloxane film, poly(L-lactic acid) film, and octadecyltrimethoxysilane-modified silicon dioxide. As a proof of concept, the gas sensor fabricated with a single reduced GO scroll is used to detect NO(2) gas with a concentration as low as 0.4 ppm.

Layer thinning and etching of mechanically exfoliated MoS2 nanosheets by thermal annealing in air.

A simple thermal annealing method for layer thinning and etching of mechanically exfoliated MoS2 nanosheets in air is reported. Using this method, single-layer (1L) MoS2 nanosheets are achieved after the thinning of MoS2 nanosheets from double-layer (2L) to quadri-layer (4L) at 330 °C. The as-prepared 1L MoS2 nanosheet shows comparable optical and electrical properties with the mechanically exfoliated, pristine one. In addition, for the first time, the MoS2 mesh with high-density of triangular pits is also fabricated at 330 °C, which might arise from the anisotropic etching of the active MoS2 edge sites. As a result of thermal annealing in air, the thinning of MoS2 nanosheet is possible due to its oxidation to form MoO3 . Importantly, the MoO3 fragments on the top of thinned MoS2 layer induces the hole injection, resulting in the p-type channel in fabricated field-effect transistors.

Nanostructured Free-Form Objects via a Synergy of 3D Printing and Thermal Nanoimprinting.

High-resolution surface patterning has garnered interests as a nonchemical-based surface engineering approach for creating functional surfaces. Applications in consumer products, parts for transportation vehicles, optics, and biomedical technologies demand topographic patterning on 3D net shape objects. Through a hybrid approach, high-resolution surface texture is incorporated onto 3D-printed polymers via direct thermal nanoimprinting process. The synergy of geometry design freedom in 3D printing and the high spatial resolution in nanoimprinting is demonstrated to be a versatile fabrication of high-fidelity surface pattern (from 2 µm to 200 nm resolution) on convex, concave semicylindrical, and hemispherical objects spanning a range of surface curvatures. The novel hybrid fabrication is further extended to achieve a high-resolution curved mold insert for rapid prototyping via injection molding. The versatility of the fabrication strategies reported here not only provides a post-3D printing process that enhances the surface properties of 3D-printed objects but also opens a new pathway to enable future study on the effects of combining microscale and nanoscale surface texture with macroscopic curvature. Both have been known, individually, as an effective approach to tune surface functionalities.

Surface modification-induced phase transformation of hexagonal close-packed gold square sheets.

Conventionally, the phase transformation of inorganic nanocrystals is realized under extreme conditions (for example, high temperature or high pressure). Here we report the complete phase transformation of Au square sheets (AuSSs) from hexagonal close-packed (hcp) to face-centered cubic (fcc) structures at ambient conditions via surface ligand exchange, resulting in the formation of (100)f-oriented fcc AuSSs. Importantly, the phase transformation can also be realized through the coating of a thin metal film (for example, Ag) on hcp AuSSs. Depending on the surfactants used during the metal coating process, two transformation pathways are observed, leading to the formation of (100)f-oriented fcc Au@Ag core-shell square sheets and (110)h/(101)f-oriented hcp/fcc mixed Au@Ag nanosheets. Furthermore, monochromated electron energy loss spectroscopy reveals the strong surface plasmon resonance absorption of fcc AuSS and Au@Ag square sheet in the infrared region. Our findings may offer a new route for the crystal-phase and shape-controlled synthesis of inorganic nanocrystals.

Stabilization of 4H hexagonal phase in gold nanoribbons.

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.

A universal, rapid method for clean transfer of nanostructures onto various substrates.

Transfer and integration of nanostructures onto target substrates is the prerequisite for their fundamental studies and practical applications. Conventional transfer techniques that involve stamping, lift-off, and/or striping suffer from the process-specific drawbacks, such as the requirement for chemical etchant or high-temperature annealing and the introduction of surface discontinuities and/or contaminations that can greatly hinder the properties and functions of the transferred materials. Herein, we report a universal and rapid transfer method implementable at mild conditions. Nanostructures with various dimensionalities (i.e., nanoparticles, nanowires, and nanosheets) and surface properties (i.e., hydrophilic and hydrophobic) can be easily transferred to diverse substrates including hydrophilic, hydrophobic, and flexible surfaces with good fidelity. Importantly, our method ensures the rapid and clean transfer of two-dimensional materials and allows for the facile fabrication of vertical heterostructures with various compositions used for electronic devices. We believe that our method can facilitate the development of nanoelectronics by accelerating the clean transfer and integration of low-dimensional materials into multidimensional structures.

The mechanical behavior and biocompatibility of polymer blends for Patent Ductus Arteriosus (PDA) occlusion device.

Patent Ductus Arteriosus (PDA) is a cardiovascular defect that occurs in 1 out of every 2000 births, and if left untreated, may lead to severe cardiovascular problems. Current options for occluding utilize meta scaffolds with polymer fabric, and are permanent. The purpose of this study was to develop a fully degradable occluder for the closure of PDA, that can be deployed percutaneously without open-heart surgery. For percutaneous deployment, both elasticity and sufficient mechanical strength are required of the device components. As this combination of properties is not achievable with currently-available homo- or copolymers, blends of biodegradable poly(ε-caprolactone) (PCL) and poly(L-lactide-co-ε-caprolactone) (PLC) with various compositions were studied as the potential material for the PDA occlusion device. Microstructures of this blend were characterized by differential scanning calorimetry (DSC) and tensile tests. DSC results demonstrated the immiscibility between PCL and its copolymer PLC. Furthermore, the mechanical properties, i.e. elastic modulus and strain recovery, of the blends could be largely tailored by changing the continuous phase component. Based on the thermo-mechanical tests, suitable blends were selected to fabricate a prototype of PDA occluder and its in vitro performance, in term of device recovery (from its sheathed configuration), biodegradation rate and blood compatibility, was evaluated. The current results indicate that the device is able to recover elastically from a sheath within 2-3min for deployment; the device starts to disintegrate within 5-6 months, and the materials have no adverse effects on the platelet and leucocyte components of the blood. Biocompatibility implantation studies of the device showed acceptable tissue response. Finally, an artificial PDA conduit was created in a pig model, and the device deployment was tested from a sheath: the device recovered within 2-3min of unsheathing and fully sealed the conduit, the device remains stable and is completely covered by tissue at 1 month follow up. Thus, a novel prototype for PDA occlusion that is fully degradable has been developed to overcome the limitations of the currently used metal/fabric devices.

Investigation of MoS2 and graphene nanosheets by magnetic force microscopy.

For the first time, magnetic force microscopy (MFM) is used to characterize the mechanically exfoliated single- and few-layer MoS2 and graphene nanosheets. By analysis of the phase and amplitude shifts, the magnetic response of MoS2 and graphene nanosheets exhibits the dependence on their layer number. However, the solution-processed single-layer MoS2 nanosheet shows the reverse magnetic signal to the mechanically exfoliated one, and the graphene oxide nanosheet has not shown any detectable magnetic signal. Importantly, graphene and MoS2 flakes become nonmagnetic when they exceed a certain thickness.

Rapid and reliable thickness identification of two-dimensional nanosheets using optical microscopy.

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.

Surface modification of smooth poly(L-lactic acid) films for gelatin immobilization.

Poly(L-lactic acid) (PLLA) is widely used in drug delivery and medical implants. Surface modification of PLLA with functional groups to immobilize gelatin or other extracellular matrix proteins is commonly used to improve its cellular affinity. In this work, we use the oxygen plasma to treat PLLA film followed by modification with organosilanes with different functional groups, such as amine, epoxy, and aldehyde groups. Gelatin is then immobilized on the modified PLLA film, which is confirmed by water contact angle measurement, atomic force microscopy (AFM), and laser scanning confocal microscopy (LSCM). Among the used organosilanes, aminosilane is the best one for modification of PLLA used for immobilization of gelatin with the highest efficiency. Moreover, the cellular affinity of gelatin-immobilized PLLA is studied through the evaluation of cell proliferation and focal adhesion using the human umbilical vein endothelial cells (HUVECs). Our experimental results show that the gelatin immobilized on aminosilane- and aldehyde-silane-modified PLLA improves the cellular affinity of HUVECs, whereas that immobilized on epoxy-silane-modified PLLA does not show significant improvement on the cell proliferation.