Chemical Stabilization of 1T' Phase Transition Metal Dichalcogenides with Giant Optical Kerr Nonlinearity.

The 2H-to-1T' phase transition in transition metal dichalcogenides (TMDs) has been exploited to phase-engineer TMDs for applications in which the metallicity of the 1T' phase is beneficial. However, phase-engineered 1T'-TMDs are metastable; thus, stabilization of the 1T' phase remains an important challenge to overcome before its properties can be exploited. Herein, we performed a systematic study of the 2H-to-1T' phase evolution by lithiation in ultrahigh vacuum. We discovered that by hydrogenating the intercalated Li to form lithium hydride (LiH), unprecedented long-term (>3 months) air stability of the 1T' phase can be achieved. Most importantly, this passivation method has wide applicability for other alkali metals and TMDs. Density functional theory calculations reveal that LiH is a good electron donor and stabilizes the 1T' phase against 2H conversion, aided by the formation of a greatly enhanced interlayer dipole-dipole interaction. Nonlinear optical studies reveal that air-stable 1T'-TMDs exhibit much stronger optical Kerr nonlinearity and higher optical transparency than the 2H phase, which is promising for nonlinear photonic applications.

Substoichiometric Molybdenum Sulfide Phases with Catalytically Active Basal Planes.

Molybdenum sulfide (MoS2) is widely recognized for its catalytic activities where the edges of the crystals turn over reactions. Generating sulfur defects on the basal plane of MoS2 can improve its catalytic activity, but generally, there is a lack of model systems for understanding metal-centered catalysis on the basal planes. Here, we synthesized a new phase of substoichiometric molybdenum sulfide (s-MoSx) on a sulfur-enriched copper substrate. The basal plane of s-MoSx contains chemically reactive Mo-rich sites that can undergo dynamic dissociative adsorption/desorption processes with molecular hydrogen, thus demonstrating its usefulness for hydrogen-transfer catalysis. In addition, scanning tunneling microscopy was used to monitor surface-directed Ullmann coupling of 2,8-dibromo-dibenzothiophene molecules on s-MoSx nanosheets, where the 4-fold symmetric surface sites on s-MoSx direct C-C coupling to form cyclic tetramers with high selectivity.

Tandem catalysis of amines using porous graphene oxide.

Porous graphene oxide can be used as a metal-free catalyst in the presence of air for oxidative coupling of primary amines. Herein, we explore a GO-catalyzed carbon-carbon or/and carbon-heteroatom bond formation strategy to functionalize primary amines in tandem to produce a series of valuable products, i.e., α-aminophosphonates, α-aminonitriles, and polycyclic heterocompounds. Furthermore, when decorated with nano-Pd, the Pd-coated porous graphene oxide can be used as a bifunctional catalyst for tandem oxidation and hydrogenation reactions in the N-alkylation of primary amines, achieving good to excellent yields under mild conditions.

Ultrahigh Capacity Due to Multi-Electron Conversion Reaction in Reduced Graphene Oxide-Wrapped MoO2 Porous Nanobelts.

Multivalent transition metal oxides (MOx ) containing redox centers which can theoretically accept more than one electron have been suggested as promising anode materials for high-performance lithium ion batteries (LIBs). The Li-storage mechanism of these oxides is suggested to involve an unusual conversion reaction leading to the formation of metallic nanograins and Li2 O; however, a full-scale conversion reaction is seldom observed in molybdenum dioxide (MoO2 ) at room temperature due to slow kinetics. Herein, a full-scale multi-electron conversion reaction, leading to a high reversible capacity (974 mA h g(-1) charging capacity at 60 mA g(-1) ) in LIBs, is realized in a hybrid consisting of reduced graphene oxide (rGO) sheet-wrapped MoO2 porous nanobelts (rGO/MoO2 NBs). The rGO wrapping layers stabilize the nanophase transition in MoO2 and alleviate volume swing effects during lithiation/delithiation processes. This enables the hybrid to exhibit great cycle stability (tested to around 1900 cycles) and ultrafast rate capability (tested up to 50 A g(-1) ).

What does annealing do to metal-graphene contacts?

Annealing is a postprocessing treatment commonly used to improve metal-graphene contacts with the assumption that resist residues sandwiched at the metal-graphene contacts are removed during annealing. Here, we examine this assumption by undertaking a systematic study to understand mechanisms that lead to the contact enhancement brought about by annealing. Using a soft shadow-mask, we fabricated residue-free metal-graphene contacts with the same dimensions as lithographically defined metal-graphene contacts on the same graphene flake. Both cases show comparable contact enhancement for nickel-graphene contacts after annealing treatment signifying that removal of resist residues is not the main factor for contact enhancement. It is found instead that carbon dissolves from graphene into the metal at chemisorbed Ni- and Co-graphene interfaces and leads to many end-contacts being formed between the metal and the dangling carbon bonds in the graphene, which contributes to much smaller contact resistance.

A two-dimensional conjugated aromatic polymer via C-C coupling reaction.

The fabrication of crystalline 2D conjugated polymers with well-defined repeating units and in-built porosity presents a significant challenge to synthetic chemists. Yet they present an appealing target because of their desirable physical and electronic properties. Here we report the preparation of a 2D conjugated aromatic polymer synthesized via C-C coupling reactions between tetrabromopolyaromatic monomers. Pre-arranged monomers in the bulk crystal undergo C-C coupling driven by endogenous solid-state polymerization to produce a crystalline polymer, which can be mechanically exfoliated into micrometre-sized lamellar sheets with a thickness of 1 nm. Isothermal gas-sorption measurements of the bulk material reveal a dominant pore size of ~0.6 nm, which indicates uniform open channels from the eclipsed stacking of the sheets. When employed as an organic anode in an ambient-temperature sodium cell, the material allows a fast charge/discharge of sodium ions, with impressive reversible capacity, rate capability and stability metrics.

Analyzing Dirac Cone and Phonon Dispersion in Highly Oriented Nanocrystalline Graphene.

Chemical vapor deposition (CVD) is one of the most promising growth techniques to scale up the production of monolayer graphene. At present, there are intense efforts to control the orientation of graphene grains during CVD, motivated by the fact that there is a higher probability for oriented grains to achieve seamless merging, forming a large single crystal. However, it is still challenging to produce single-crystal graphene with no grain boundaries over macroscopic length scales, especially when the nucleation density of graphene nuclei is high. Nonetheless, nanocrystalline graphene with highly oriented grains may exhibit single-crystal-like properties. Herein, we investigate the spectroscopic signatures of graphene film containing highly oriented, nanosized grains (20-150 nm) using angle-resolved photoemission spectroscopy (ARPES) and high-resolution electron energy loss spectroscopy (HREELS). The robustness of the Dirac cone, as well as dispersion of its phonons, as a function of graphene's grain size and before and after film coalescence, was investigated. In view of the sensitivity of atomically thin graphene to atmospheric adsorbates and intercalants, ARPES and HREELS were also used to monitor the changes in spectroscopic signatures of the graphene film following exposure to the ambient atmosphere.

Phase Restructuring in Transition Metal Dichalcogenides for Highly Stable Energy Storage.

Achieving homogeneous phase transition and uniform charge distribution is essential for good cycle stability and high capacity when phase conversion materials are used as electrodes. Herein, we show that chemical lithiation of bulk 2H-MoS2 distorts its crystalline domains in three primary directions to produce mosaic-like 1T' nanocrystalline domains, which improve phase and charge uniformity during subsequent electrochemical phase conversion. 1T'-LixMoS2, a macroscopic dense material with interconnected nanoscale grains, shows excellent cycle stability and rate capability in a lithium rechargeable battery compared to bulk or exfoliated-restacked MoS2. Transmission electron microscopy studies reveal that the interconnected MoS2 nanocrystals created during the phase change process are reformable even after multiple cycles of galvanostatic charging/discharging, which allows them to play important roles in the long term cycling performance of the chemically intercalated TMD materials. These studies shed light on how bulk TMDs can be processed into quasi-2D nanophase material for stable energy storage.

Oscillating edge states in one-dimensional MoS2 nanowires.

Reducing the dimensionality of transition metal dichalcogenides to one dimension opens it to structural and electronic modulation related to charge density wave and quantum correlation effects arising from edge states. The greater flexibility of a molecular scale nanowire allows a strain-imposing substrate to exert structural and electronic modulation on it, leading to an interplay between the curvature-induced influences and intrinsic ground-state topology. Herein, the templated growth of MoS2 nanowire arrays consisting of the smallest stoichiometric MoS2 building blocks is investigated using scanning tunnelling microscopy and non-contact atomic force microscopy. Our results show that lattice strain imposed on a nanowire causes the energy of the edge states to oscillate periodically along its length in phase with the period of the substrate topographical modulation. This periodic oscillation vanishes when individual MoS2 nanowires join to form a wider nanoribbon, revealing that the strain-induced modulation depends on in-plane rigidity, which increases with system size.

Wafer-Scale Single-Crystalline AB-Stacked Bilayer Graphene.

Single-crystalline artificial AB-stacked bilayer graphene is formed by aligned transfer of two single-crystalline monolayers on a wafer-scale. The obtained bilayer has a well-defined interface and is electronically equivalent to exfoliated or direct-grown AB-stacked bilayers.

Studying Edge Defects of Hexagonal Boron Nitride Using High-Resolution Electron Energy Loss Spectroscopy.

Studying the phonons of hexagonal boron nitride (h-BN) is important for understanding its thermal, electronic, and imaging applications. Herein, we applied high-resolution electron energy loss spectroscopy (HREELS) to monitor the presence of edge defects in h-BN films. We observed an edge phonon at 90.5 meV with the initial formation of island-like domains on Ru(0001), which subsequently weakens with respect to the bulk phonon as the islands congregate into a film. The presence of a weak edge phonon peak even at full surface coverage of the h-BN film indicates the sensitivity of HREELS in detecting line defects. A shoulder peak at ∼160 meV assignable to sp(3) bonded modes was attributed to grain boundaries arising from misaligned domains. In addition, the strengths of substrate interaction and the rippling of the h-BN film can be judged from the shift in the phonon energy of the out-of-plane TO⊥ mode.

Tuning the threshold voltage of MoS2 field-effect transistors via surface treatment.

Controlling the threshold voltage (Vth) of a field-effect transistor is important for realizing robust logic circuits. Here, we report a facile approach to achieve bidirectional Vth tuning of molybdenum disulfide (MoS2) field-effect transistors. By increasing and decreasing the amount of sulfur vacancies in the MoS2 surface, the Vth of MoS2 transistors can be left- and right-shifted, respectively. Transistors fabricated on perfect MoS2 flakes are found to exhibit a two-fold enhancement in mobility and a very positive Vth (18.5 ± 7.5 V). More importantly, our elegant hydrogen treatment is able to tune the large Vth to a small value (∼0 V) without any performance degradation simply by reducing the atomic ratio of S : Mo slightly; in other words, it creates a certain amount of sulfur vacancies in the MoS2 surface, which generate defect states in the band gap of MoS2 that mediates conduction of a MoS2 transistor in the subthreshold regime. First-principles calculations further indicate that the defect band's edge and width can be tuned according to the vacancy density. This work not only demonstrates for the first time the ease of tuning the Vth of MoS2 transistors, but also offers a process technology solution that is critical for further development of MoS2 as a mainstream electronic material.

Chemical Vapor Deposition of Large-Sized Hexagonal WSe2 Crystals on Dielectric Substrates.

High-quality large-sized hexagoal WSe2 crystals can be grown on dielectric substrates using atmospheric chemical vapor deposition in the presence of hydrogen gas. These hexagonal crystals (lateral width >160 um) have a carrier mobility of 100 cm(2) V(-1) s(-1) and a photoresponsivity of ≈1100 mA W(-1), which is comparable to that of exfoliated flakes.

High yield exfoliation of two-dimensional chalcogenides using sodium naphthalenide.

Transition-metal dichalcogenides like molybdenum disulphide have attracted great interest as two-dimensional materials beyond graphene due to their unique electronic and optical properties. Solution-phase processes can be a viable method for producing printable single-layer chalcogenides. Molybdenum disulphide can be exfoliated into monolayer flakes using organolithium reduction chemistry; unfortunately, the method is hampered by low yield, submicron flake size and long lithiation time. Here we report a high-yield exfoliation process using lithium, potassium and sodium naphthalenide where an intermediate ternary Li(x)MX(n) crystalline phase (X=selenium, sulphur, and so on) is produced. Using a two-step expansion and intercalation method, we produce high-quality single-layer molybdenum disulphide sheets with unprecedentedly large flake size, that is up to 400 µm(2). Single-layer dichalcogenide inks prepared by this method may be directly inkjet-printed on a wide range of substrates.

Giant enhancement in vertical conductivity of stacked CVD graphene sheets by self-assembled molecular layers.

Layer-by-layer-stacked chemical vapour deposition (CVD) graphene films find applications as transparent and conductive electrodes in solar cells, organic light-emitting diodes and touch panels. Common to lamellar-type systems with anisotropic electron delocalization, the plane-to-plane (vertical) conductivity in such systems is several orders lower than its in-plane conductivity. The poor electronic coupling between the planes is due to the presence of transfer process organic residues and trapped air pocket in wrinkles. Here we show the plane-to-plane tunnelling conductivity of stacked CVD graphene layers can be improved significantly by inserting 1-pyrenebutyric acid N-hydroxysuccinimide ester between the graphene layers. The six orders of magnitude increase in plane-to-plane conductivity is due to hole doping, orbital hybridization, planarization and the exclusion of polymer residues. Our results highlight the importance of interfacial modification for enhancing the performance of LBL-stacked CVD graphene films, which should be applicable to other types of stacked two-dimensional films.

Graphene Oxide-Polythiophene Hybrid with Broad-Band Absorption and Photocatalytic Properties.

Hybrid graphene oxide (GO)/poly(3-hexylthiophene-2,5-diyl) (P3HT) sheets are assembled via π-π interaction and carefully isolated from the nonreacted precursors. The mutual influence of the two phases can be sharply manifested in this layer-to-layer configuration because it is undiluted by excess of one phase. To investigate the optical properties of the hybrid and possible synergistic interactions, we applied photothermal deflection spectroscopy (PDS) and pump-probe techniques. For the first time, the photocatalytic performance of these hybrids was investigated to correlate with their optical properties. The GO-P3HT hybrid demonstrates broad-band absorption and ultrafast charge transfer (1.4 ps) and acts as an excellent photocatalyst for the Mannich reaction (93% yield).