Zhuhua Zhang

Generating electricity by moving a droplet of ionic liquid along graphene

Since the early nineteenth century, it has been known that an electric potential can be generated by driving an ionic liquid through fine channels or holes under a pressure gradient. More recently, it has been reported that carbon nanotubes can generate a voltage when immersed in flowing liquids, but the exact origin of these observations is unclear, and generating electricity without a pressure gradient remains a challenge. Here, we show that a voltage of a few millivolts can be produced by moving a droplet of sea water or ionic solution over a strip of monolayer graphene under ambient conditions. Through experiments and density functional theory calculations, we find that a pseudocapacitor is formed at the droplet/graphene interface, which is driven forward by the moving droplet, charging and discharging at the front and rear of the droplet. This gives rise to an electric potential that is proportional to the velocity and number of droplets. The potential is also found to be dependent on the concentration and ionic species of the droplet, and decreases sharply with an increasing number of graphene layers. We illustrate the potential of this electrokinetic phenomenon by using it to create a handwriting sensor and an energy-harvesting device.

Top–down fabrication of sub-nanometre semiconducting nanoribbons derived from molybdenum disulfide sheets

Developments in semiconductor technology are propelling the dimensions of devices down to 10 nm, but facing great challenges in manufacture at the sub-10 nm scale. Nanotechnology can fabricate nanoribbons from two-dimensional atomic crystals, such as graphene, with widths below the 10 nm threshold, but their geometries and properties have been hard to control at this scale. Here we find that robust ultrafine molybdenum-sulfide ribbons with a uniform width of 0.35 nm can be widely formed between holes created in a MoS2 sheet under electron irradiation. In situ high-resolution transmission electron microscope characterization, combined with first-principles calculations, identifies the sub-1 nm ribbon as a Mo5S4 crystal derived from MoS2, through a spontaneous phase transition. Further first-principles investigations show that the Mo5S4 ribbon has a band gap of 0.77 eV, a Young’s modulus of 300GPa and can demonstrate 9% tensile strain before fracture. The results show a novel top–down route for controllable fabrication of functional building blocks for sub-nanometre electronics.

Direct chemical conversion of graphene to boron- and nitrogen- and carbon-containing atomic layers

Graphene and hexagonal boron nitride are typical conductor and insulator, respectively, while their hybrids hexagonal boron carbonitride are promising as a semiconductor. Here we demonstrate a direct chemical conversion reaction, which systematically converts the hexagonal carbon lattice of graphene to boron nitride, making it possible to produce uniform boron nitride and boron carbonitride structures without disrupting the structural integrity of the original graphene templates. We synthesize high-quality atomic layer films with boron-, nitrogen- and carbon-containing atomic layers with full range of compositions. Using this approach, the electrical resistance, carrier mobilities and bandgaps of these atomic layers can be tuned from conductor to semiconductor to insulator. Combining this technique with lithography, local conversion could be realized at the nanometre scale, enabling the fabrication of in-plane atomic layer structures consisting of graphene, boron nitride and boron carbonitride. This is a step towards scalable synthesis of atomically thin two-dimensional integrated circuits.

Intrinsic Magnetism of Grain Boundaries in Two-Dimensional Metal Dichalcogenides

Grain boundaries (GBs) are structural imperfections that typically degrade the performance of materials. Here we show that dislocations and GBs in two-dimensional (2D) metal dichalcogenides MX2 (M = Mo, W; X = S, Se) can actually improve the material by giving it a qualitatively new physical property: magnetism. The dislocations studied all display a substantial magnetic moment of ∼1 Bohr magneton. In contrast, dislocations in other well-studied 2D materials are typically nonmagnetic. GBs composed of pentagon-heptagon pairs interact ferromagnetically and transition from semiconductor to half-metal or metal as a function of tilt angle and/or doping level. When the tilt angle exceeds 47°, the structural energetics favor square-octagon pairs and the GB becomes an antiferromagnetic semiconductor. These exceptional magnetic properties arise from interplay of dislocation-induced localized states, doping, and locally unbalanced stoichiometry. Purposeful engineering of topological GBs may be able to convert MX2 into a promising 2D magnetic semiconductor.

Two-Dimensional Tetragonal TiC Monolayer Sheet and Nanoribbons

We report a two-dimensional tetragonal Titanium Carbide (TiC) monolayer sheet with distinguished structure and properties based on comprehensive first-principles calculations. The TiC sheet exhibits a novel zigzag-shaped buckling structure with all atoms being quasiplanar tetracoordinate, as favored by strong in-plane C2p-Ti3d bonding and synergetic out-of-plane electronic delocalization. This unique structure endows the sheet with high kinetic stability and anisotropic mechanical properties. Moreover, the TiC sheet displays orientation-dependent electronic properties derived from its special rectangular symmetry, with indirect band gap of ~0.2 eV and substantial ferromagnetism along its edges, thus promising for wide applications in nanoelectronics.

Two-Dimensional Boron Monolayers Mediated by Metal Substrates

Two-dimensional (2D) materials, such as graphene and boron nitride, have specific lattice structures independent of external conditions. In contrast, the structure of 2D boron sensitively depends on metal substrate, as we show herein using the cluster expansion method and a newly developed surface structure-search method, both based on first-principles calculations. The preferred 2D boron on weaker interacting Au is nonplanar with significant buckling and numerous polymorphs as in vacuum, whereas on more reactive Ag, Cu, and Ni, the polymorphic energy degeneracy is lifted and a particular planar structure is found to be most stable. We also show that a layer composed of icosahedral B12 is unfavorable on Cu and Ni but unexpectedly becomes a possible minimum on Au and Ag. The substrate-dependent 2D boron choices originate from a competition between the strain energy of buckling and chemical energy of electronic hybridization between boron and metal.

Photoluminescence Quenching and Charge Transfer in Artificial Heterostacks of Monolayer Transition Metal Dichalcogenides and Few-Layer Black Phosphorus

Transition metal dichalcogenides monolayers and black phosphorus thin crystals are emerging two-dimensional materials that demonstrated extraordinary optoelectronic properties. Exotic properties and physics may arise when atomic layers of different materials are stacked together to form van der Waals solids. Understanding the important interlayer couplings in such heterostructures could provide avenues for control and creation of characteristics in these artificial stacks. Here we systematically investigate the optical and optoelectronic properties of artificial stacks of molybdenum disulfide, tungsten disulfide, and black phosphorus atomic layers. An anomalous photoluminescence quenching was observed in tungsten disulfide-molybdenum disulfide stacks. This was attributed to a direct to indirect band gap transition of tungsten disulfide in such stacks while molybdenum disulfide maintains its monolayer properties by first-principles calculations. On the other hand, due to the strong build-in electric fields in tungsten disulfide-black phosphorus or molybdenum disulfide-black phosphorus stacks, the excitons can be efficiently splitted despite both the component layers having a direct band gap in these stacks. We further examine optoelectronic properties of tungsten disulfide-molybdenum disulfide artificial stacks and demonstrate their great potentials in future optoelectronic applications.

Harvesting Energy from Water Flow over Graphene

It is reported excitingly in a previous letter (Nano Lett. 2011, 11, 3123) that a small piece of graphene sheet about 30 × 16 μm(2) immersed in flowing water with 0.6 M hydrochloric acid can produce voltage ~20 mV. Here we find that no measurable voltage can be induced by the flow over mono-, bi- and trilayered graphene samples of ~1 × 1.5 cm(2) in size in the same solution once the electrodes on graphene are isolated from interacting with the solution, mainly because the H(3)O(+) cations in the water adsorb onto graphene by strong covalent bonds as revealed by our first-principles calculations. When both the graphene and its metal electrodes are exposed to the solution as in the previous work, water flow over the graphene-electrode system can induce voltages from a few to over a hundred millivolts. In this situation, the graphene mainly behaves as a load connecting between the electrodes. Therefore, the harvested energy is not from the immersed carbon nanomaterials themselves in ionic water flow but dominated by the exposed electrodes.

Tunable ferromagnetic spin ordering in boron nitride nanotubes with topological fluorine adsorption.

We find through first-principles calculations that fluorine atoms topologically adsorbed on boron nitride nanotubes induce long-ranged ferromagnetic spin ordering along the tube, offering strong spin polarization around the Fermi level. The spin polarization and magnetic moment increase significantly with decreasing tube radius, even giving rise to half-metal when the tube diameter is reduced to 3.3 A, while in a flat boron nitride sheet with the same topological fluorine arrangement the magnetic moment nearly disappears. This radius-dependent behavior is then developed into a local curvature modulation procedure to efficiently enhance or quench the ferromagnetic ordering, which enables the F-BNNTs to function as piezomagnetic nanotubes. These findings suggest a new route to facilitate the design of tunable spin devices.

Dislocation motion and grain boundary migration in two-dimensional tungsten disulphide

Dislocations have a significant effect on mechanical, electronic, magnetic and optical properties of crystals. For a dislocation to migrate in bulk crystals, collective and simultaneous movement of several atoms is needed. In two-dimensional crystals, in contrast, dislocations occur on the surface and can exhibit unique migration dynamics. Dislocation migration has recently been studied in graphene, but no studies have been reported on dislocation dynamics for two-dimensional transition metal dichalcogenides with unique metal-ligand bonding and a three-atom thickness. This study presents dislocation motion, glide and climb, leading to grain boundary migration in a tungsten disulphide monolayer. Direct atomic-scale imaging coupled with atomistic simulations reveals a strikingly low-energy barrier for glide, leading to significant grain boundary reconstruction in tungsten disulphide. The observed dynamics are unique and different from those reported for graphene. Through strain field mapping, we also demonstrate how dislocations introduce considerable strain along the grain boundaries and at the dislocation cores.