Ruitao Lv

Extraordinary Room-Temperature Photoluminescence in Triangular WS2 Monolayers

Individual monolayers of metal dichalcogenides are atomically thin two-dimensional crystals with attractive physical properties different from those of their bulk counterparts. Here we describe the direct synthesis of WS2 monolayers with triangular morphologies and strong room-temperature photoluminescence (PL). The Raman response as well as the luminescence as a function of the number of S-W-S layers is also reported. The PL weakens with increasing number of layers due to a transition from direct band gap in a monolayer to indirect gap in multilayers. The edges of WS2 monolayers exhibit PL signals with extraordinary intensity, around 25 times stronger than that at the platelets center. The structure and chemical composition of the platelet edges appear to be critical for PL enhancement.

Transition metal dichalcogenides and beyond: synthesis, properties, and applications of single- and few-layer nanosheets.

CONSPECTUS: In the wake of the discovery of the remarkable electronic and physical properties of graphene, a vibrant research area on two-dimensional (2D) layered materials has emerged during the past decade. Transition metal dichalcogenides (TMDs) represent an alternative group of 2D layered materials that differ from the semimetallic character of graphene. They exhibit diverse properties that depend on their composition and can be semiconductors (e.g., MoS2, WS2), semimetals (e.g., WTe2, TiSe2), true metals (e.g., NbS2, VSe2), and superconductors (e.g., NbSe2, TaS2). The properties of TMDs can also be tailored according to the crystalline structure and the number and stacking sequence of layers in their crystals and thin films. For example, 2H-MoS2 is semiconducting, whereas 1T-MoS2 is metallic. Bulk 2H-MoS2 possesses an indirect band gap, but when 2H-MoS2 is exfoliated into monolayers, it exhibits direct electronic and optical band gaps, which leads to enhanced photoluminescence. Therefore, it is important to learn to control the growth of 2D TMD structures in order to exploit their properties in energy conversion and storage, catalysis, sensing, memory devices, and other applications. In this Account, we first introduce the history and structural basics of TMDs. We then briefly introduce the Raman fingerprints of TMDs of different layer numbers. Then, we summarize our progress on the controlled synthesis of 2D layered materials using wet chemical approaches, chemical exfoliation, and chemical vapor deposition (CVD). It is now possible to control the number of layers when synthesizing these materials, and novel van der Waals heterostructures (e.g., MoS2/graphene, WSe2/graphene, hBN/graphene) have recently been successfully assembled. Finally, the unique optical, electrical, photovoltaic, and catalytic properties of few-layered TMDs are summarized and discussed. In particular, their enhanced photoluminescence (PL), photosensing, photovoltaic conversion, and hydrogen evolution reaction (HER) catalysis are discussed in detail. Finally, challenges along each direction are described. For instance, how to grow perfect single crystalline monolayer TMDs without the presence of grain boundaries and dislocations is still an open question. Moreover, the morphology and crystal structure control of few-layered TMDs still requires further research. For wet chemical approaches and chemical exfoliation methods, it is still a significant challenge to control the lateral growth of TMDs without expansion in the c-axis direction. In fact, there is plenty of room in the 2D world beyond graphene. We envisage that with increasing progress in the controlled synthesis of these systems the unusual properties of mono- and few-layered TMDs and TMD heterostructures will be unveiled.

Nitrogen-doped graphene: beyond single substitution and enhanced molecular sensing.

Graphene is a two-dimensional network in which sp2-hybridized carbon atoms are arranged in two different triangular sub-lattices (A and B). By incorporating nitrogen atoms into graphene, its physico-chemical properties could be significantly altered depending on the doping configuration within the sub-lattices. Here, we describe the synthesis of large-area, highly-crystalline monolayer N-doped graphene (NG) sheets via atmospheric-pressure chemical vapor deposition, yielding a unique N-doping site composed of two quasi-adjacent substitutional nitrogen atoms within the same graphene sub-lattice (N2AA). Scanning tunneling microscopy and spectroscopy (STM and STS) of NG revealed the presence of localized states in the conduction band induced by N2AA-doping, which was confirmed by ab initio calculations. Furthermore, we demonstrated for the first time that NG could be used to efficiently probe organic molecules via a highly improved graphene enhanced Raman scattering.

Controlled synthesis and transfer of large-area WS2 sheets: from single layer to few layers.

The isolation of few-layered transition metal dichalcogenides has mainly been performed by mechanical and chemical exfoliation with very low yields. In this account, a controlled thermal reduction-sulfurization method is used to synthesize large-area (~1 cm(2)) WS2 sheets with thicknesses ranging from monolayers to a few layers. During synthesis, WOx thin films are first deposited on Si/SiO2 substrates, which are then sulfurized (under vacuum) at high temperatures (750-950 °C). An efficient route to transfer the synthesized WS2 films onto different substrates such as quartz and transmission electron microscopy (TEM) grids has been satisfactorily developed using concentrated HF. Samples with different thicknesses have been analyzed by Raman spectroscopy and TEM, and their photoluminescence properties have been evaluated. We demonstrated the presence of single-, bi-, and few-layered WS2 on as-grown samples. It is well known that the electronic structure of these materials is very sensitive to the number of layers, ranging from indirect band gap semiconductor in the bulk phase to direct band gap semiconductor in monolayers. This method has also proved successful in the synthesis of heterogeneous systems of MoS2 and WS2 layers, thus shedding light on the controlled production of heterolayered devices from transition metal chalcogenides.

Defect engineering of two-dimensional transition metal dichalcogenides

Two-dimensional transition metal dichalcogenides (TMDs), an emerging family of layered materials, have provided researchers a fertile ground for harvesting fundamental science and emergent applications. TMDs can contain a number of different structural defects in their crystal lattices which significantly alter their physico-chemical properties. Having structural defects can be either detrimental or beneficial, depending on the targeted application. Therefore, a comprehensive understanding of structural defects is required. Here we review different defects in semiconducting TMDs by summarizing: (i) the dimensionalities and atomic structures of defects; (ii) the pathways to generating structural defects during and after synthesis and, (iii) the effects of having defects on the physico-chemical properties and applications of TMDs. Thus far, significant progress has been made, although we are probably still witnessing the tip of the iceberg. A better understanding and control of defects is important in order to move forward the field of Defect Engineering in TMDs. Finally, we also provide our perspective on the challenges and opportunities in this emerging field.

Carbon nanotubes filled with ferromagnetic alloy nanowires: Lightweight and wide-band microwave absorber

Thin-walled carbon nanotubes (CNTs) filled with different ferromagnetic alloy (FeCo, FeNi, and FeCoNi) nanowires were prepared by using trichlorobenzene as carbon precursor. They were dispersed into epoxy resin and then coated onto 180×180 mm2 aluminum substrates to form microwave-absorption coatings with 2.0 mm thickness. Reflection loss exceeding −5 dB was obtained between 5 and 18 GHz for coating containing 1.3 wt % FeCo-filled CNTs. A minimum reflection loss value of −28.2 dB was achieved at 15.2 GHz in FeCoNi-filled CNTs/epoxy coating. The areal densities of coatings are only 2.35 kg/m2, which is favorable for the applications requiring low density.

Enhanced efficiency of graphene/silicon heterojunction solar cells by molecular doping

Graphene (G) films were grown on copper foils by chemical vapor deposition and transferred onto n-type silicon (Si) to form G/Si Schottky heterojunction solar cells. The power conversion efficiencies (PCEs) of the G/Si solar cells were in the range of 1.94–2.66%. Four volatile oxidants HNO3, HCl, H2O2 and SOCl2 were employed to treat the graphene films in the G/Si solar cells, and the PCEs could be greatly enhanced after being treated by all the volatile oxidants and SOCl2 doping showed the best improvement. A solar cell with an initial PCE of 2.45% could be increased to 5.95% upon SOCl2 doping treatment. The PCE stability of the volatile oxidant-treated cells was also investigated. The PCEs decreased with time, while SOCl2 and HCl showed much better PCE stability than HNO3 and H2O2.

Nitrogen-enriched electrospun porous carbon nanofiber networks as high-performance free-standing electrode materials

Nitrogen-enriched porous carbon nanofiber networks (NPCNFs) were successfully prepared by using low-cost melamine and polyacrylonitrile as precursors via electrospinning followed by carbonization and NH3 treatments. The NPCNFs exhibited inter-connected nanofibrous morphology with a large specific surface area, well-developed microporous structure, relatively high-level nitrogen doping and great amount of pyridinic nitrogen. As free-standing new anode materials in lithium-ion batteries (LIBs), the NPCNFs showed ultrahigh capacity, good cycle performance and superior rate capability with a reversible capacity of as high as 1323 mA h g−1 at a current density of 50 mA g−1. These attractive characteristics make the NPCNFs materials very promising anode candidates for high-performance LIBs and, as free-standing electrode materials to be used in other energy conversion and storage devices.

Ultrasensitive gas detection of large-area boron-doped graphene

Significance The gas-sensing performance of graphene could be remarkably enhanced by incorporating dopants into its lattice based on theoretical calculations. However, to date, experimental progress on boron-doped graphene (BG) is still very scarce. Here, we achieved the controlled growth of large-area, high-crystallinity BG sheets and shed light on their electronic features associated with boron dopants at the atomic scale. As a proof-of-concept, it is demonstrated that boron doping in graphene could lead to a much enhanced sensitivity when detecting toxic gases (e.g. NO2). Our results will open up new avenues for developing high-performance sensors able to detect trace amount of molecules. In addition, other new fascinating properties can be exploited based on as-synthesized large-area BG sheets. Heteroatom doping is an efficient way to modify the chemical and electronic properties of graphene. In particular, boron doping is expected to induce a p-type (boron)-conducting behavior to pristine (nondoped) graphene, which could lead to diverse applications. However, the experimental progress on atomic scale visualization and sensing properties of large-area boron-doped graphene (BG) sheets is still very scarce. This work describes the controlled growth of centimeter size, high-crystallinity BG sheets. Scanning tunneling microscopy and spectroscopy are used to visualize the atomic structure and the local density of states around boron dopants. It is confirmed that BG behaves as a p-type conductor and a unique croissant-like feature is frequently observed within the BG lattice, which is caused by the presence of boron-carbon trimers embedded within the hexagonal lattice. More interestingly, it is demonstrated for the first time that BG exhibits unique sensing capabilities when detecting toxic gases, such as NO2 and NH3, being able to detect extremely low concentrations (e.g., parts per trillion, parts per billion). This work envisions that other attractive applications could now be explored based on as-synthesized BG.

Facile synthesis of nitrogen-doped carbon nanosheets with hierarchical porosity for high performance supercapacitors and lithium–sulfur batteries

Magnesium citrate and potassium citrate are two commonly used food additives in our daily life. Herein, we prepared nitrogen-doped hierarchical porous carbon nanosheets (N-HPCNSs) through direct pyrolysis of their mixtures and subsequent NH3 treatment. The as-prepared N-HPCNS shows hierarchical porosity (specific surface area of 1735 m2 g−1 and pore volume of 1.71 cm3 g−1), and a moderate nitrogen doping of 1.7%. Moreover, it can be effectively applied in various energy storage/conversion systems. When used as supercapacitor electrodes, it shows a high specific capacitance of 128 F g−1 in organic electrolytes and retains 45% of the original capacitance even at an ultrahigh current density of 100 A g−1. It can also serve as an effective sulfur carrier in lithium–sulfur batteries. The N-HPCNS/sulfur cathode shows high discharge capacities of 1209 mA h g−1 at 0.2C and 493 mA h g−1 even at 4C. Over 500 charge/discharge cycles at 1C, it still retains a high discharge capacity of 486 mA h g−1 with an ultralow capacity loss of 0.051% per cycle and a high average coulombic efficiency of 99.4%.