Electron Doping of Ultrathin Black Phosphorus with Cu Adatoms.

Few-layer black phosphorus is a monatomic two-dimensional crystal with a direct band gap that has high carrier mobility for both holes and electrons. Similarly to other layered atomic crystals, like graphene or layered transition metal dichalcogenides, the transport behavior of few-layer black phosphorus is sensitive to surface impurities, adsorbates, and adatoms. Here we study the effect of Cu adatoms onto few-layer black phosphorus by characterizing few-layer black phosphorus field effect devices and by performing first-principles calculations. We find that the addition of Cu adatoms can be used to controllably n-dope few layer black phosphorus, thereby lowering the threshold voltage for n-type conduction without degrading the transport properties. We demonstrate a scalable 2D material-based complementary inverter which utilizes a boron nitride gate dielectric, a graphite gate, and a single bP crystal for both the p- and n-channels. The inverter operates at matched input and output voltages, exhibits a gain of 46, and does not require different contact metals or local electrostatic gating.

Analysis of Time-Varying, Stochastic Gas Transport through Graphene Membranes.

Molecular transport measurements through isolated nanopores can greatly inform our understanding of how such systems can select for molecular size and shape. In this work, we present a detailed analysis of experimental gas permeation data through single layer graphene membranes under batch depletion conditions parametric in starting pressure for He, H2, Ne, and CO2 between 100 and 670 kPa. We show mathematically that the observed intersections of the membrane deflection curves parametric in starting pressure are indicative of a time dependent membrane permeance (pressure normalized molecular flow). Analyzing these time dependent permeance data for He, Ne, H2, and CO2 shows remarkably that the latter three gases exhibit discretized permeance values that are temporally repeated. Such quantized fluctuations (called "gating" for liquid phase nanopore and ion channel systems) are a hallmark of isolated nanopores, since small, but rapid changes in the transport pathway necessarily influence a single detectable flux. We analyze the fluctuations using a Hidden Markov model to fit to discrete states and estimate the activation barrier for switching at 1.0 eV. This barrier is and the relative fluxes are consistent with a chemical bond rearrangement of an 8-10 atom vacancy pore. Furthermore, we use the relations between the states given by the Markov network for few pores to determine that three pores, each exhibiting two state switching, are responsible for the observed fluctuations; and we compare simulated control data sets with and without the Markov network for comparison and to establish confidence in our evaluation of the limited experimental data set.

Molecular valves for controlling gas phase transport made from discrete ångström-sized pores in graphene.

An ability to precisely regulate the quantity and location of molecular flux is of value in applications such as nanoscale three-dimensional printing, catalysis and sensor design. Barrier materials containing pores with molecular dimensions have previously been used to manipulate molecular compositions in the gas phase, but have so far been unable to offer controlled gas transport through individual pores. Here, we show that gas flux through discrete ångström-sized pores in monolayer graphene can be detected and then controlled using nanometre-sized gold clusters, which are formed on the surface of the graphene and can migrate and partially block a pore. In samples without gold clusters, we observe stochastic switching of the magnitude of the gas permeance, which we attribute to molecular rearrangements of the pore. Our molecular valves could be used, for example, to develop unique approaches to molecular synthesis that are based on the controllable switching of a molecular gas flux, reminiscent of ion channels in biological cell membranes and solid-state nanopores.

Colossal Ultraviolet Photoresponsivity of Few-Layer Black Phosphorus.

Black phosphorus has an orthorhombic layered structure with a layer-dependent direct band gap from monolayer to bulk, making this material an emerging material for photodetection. Inspired by this and the recent excitement over this material, we studied the optoelectronics characteristics of high-quality, few-layer black phosphorus-based photodetectors over a wide spectrum ranging from near-ultraviolet (UV) to near-infrared (NIR). It is demonstrated for the first time that black phosphorus can be configured as an excellent UV photodetector with a specific detectivity ∼3 × 10(13) Jones. More critically, we found that the UV photoresponsivity can be significantly enhanced to ∼9 × 10(4) A W(-1) by applying a source-drain bias (VSD) of 3 V, which is the highest ever measured in any 2D material and 10(7) times higher than the previously reported value for black phosphorus. We attribute such a colossal UV photoresponsivity to the resonant-interband transition between two specially nested valence and conduction bands. These nested bands provide an unusually high density of states for highly efficient UV absorption due to the singularity of their nature.

Transport properties of pristine few-layer black phosphorus by van der Waals passivation in an inert atmosphere.

Ultrathin black phosphorus is a two-dimensional semiconductor with a sizeable band gap. Its excellent electronic properties make it attractive for applications in transistor, logic and optoelectronic devices. However, it is also the first widely investigated two-dimensional material to undergo degradation upon exposure to ambient air. Therefore a passivation method is required to study the intrinsic material properties, understand how oxidation affects the physical properties and enable applications of phosphorene. Here we demonstrate that atomically thin graphene and hexagonal boron nitride can be used for passivation of ultrathin black phosphorus. We report that few-layer pristine black phosphorus channels passivated in an inert gas environment, without any prior exposure to air, exhibit greatly improved n-type charge transport resulting in symmetric electron and hole transconductance characteristics.

Nanometer thick elastic graphene engine.

Significant progress has been made in the construction and theoretical understanding of molecular motors because of their potential use. Here, we have demonstrated fabrication of a simple but powerful 1 nm thick graphene engine. The engine comprises a high elastic membrane-piston made of graphene and weakly chemisorbed ClF3 molecules as the high power volume changeable actuator, while a 532 nm LASER acts as the ignition plug. Rapid volume expansion of the ClF3 molecules leads to graphene blisters. The size of the blister is controllable by changing the ignition parameters. The estimated internal pressure per expansion cycle of the engine is about ∼10(6) Pa. The graphene engine presented here shows exceptional reliability, showing no degradation after 10,000 cycles.

Selective molecular sieving through porous graphene.

Membranes act as selective barriers and play an important role in processes such as cellular compartmentalization and industrial-scale chemical and gas purification. The ideal membrane should be as thin as possible to maximize flux, mechanically robust to prevent fracture, and have well-defined pore sizes to increase selectivity. Graphene is an excellent starting point for developing size-selective membranes because of its atomic thickness, high mechanical strength, relative inertness and impermeability to all standard gases. However, pores that can exclude larger molecules but allow smaller molecules to pass through would have to be introduced into the material. Here, we show that ultraviolet-induced oxidative etching can create pores in micrometre-sized graphene membranes, and the resulting membranes can be used as molecular sieves. A pressurized blister test and mechanical resonance are used to measure the transport of a range of gases (H(2), CO(2), Ar, N(2), CH(4) and SF(6)) through the pores. The experimentally measured leak rate, separation factors and Raman spectrum agree well with models based on effusion through a small number of ångstrom-sized pores.

Ultrathin oxide films by atomic layer deposition on graphene.

In this paper, a method is presented to create and characterize mechanically robust, free-standing, ultrathin, oxide films with controlled, nanometer-scale thickness using atomic layer deposition (ALD) on graphene. Aluminum oxide films were deposited onto suspended graphene membranes using ALD. Subsequent etching of the graphene left pure aluminum oxide films only a few atoms in thickness. A pressurized blister test was used to determine that these ultrathin films have a Young's modulus of 154 ± 13 GPa. This Young's modulus is comparable to much thicker alumina ALD films. This behavior indicates that these ultrathin two-dimensional films have excellent mechanical integrity. The films are also impermeable to standard gases suggesting they are pinhole-free. These continuous ultrathin films are expected to enable new applications in fields such as thin film coatings, membranes, and flexible electronics.

Ultrastrong adhesion of graphene membranes.

As mechanical structures enter the nanoscale regime, the influence of van der Waals forces increases. Graphene is attractive for nanomechanical systems because its Young's modulus and strength are both intrinsically high, but the mechanical behaviour of graphene is also strongly influenced by the van der Waals force. For example, this force clamps graphene samples to substrates, and also holds together the individual graphene sheets in multilayer samples. Here we use a pressurized blister test to directly measure the adhesion energy of graphene sheets with a silicon oxide substrate. We find an adhesion energy of 0.45±0.02 J m(-2) for monolayer graphene and 0.31±0.03 J m(-2) for samples containing two to five graphene sheets. These values are larger than the adhesion energies measured in typical micromechanical structures and are comparable to solid-liquid adhesion energies. We attribute this to the extreme flexibility of graphene, which allows it to conform to the topography of even the smoothest substrates, thus making its interaction with the substrate more liquid-like than solid-like.