Christopher R. Ryder

Covalent functionalization and passivation of exfoliated black phosphorus via aryl diazonium chemistry

Functionalization of atomically thin nanomaterials enables the tailoring of their chemical, optical and electronic properties. Exfoliated black phosphorus (BP)-a layered two-dimensional semiconductor-exhibits favourable charge-carrier mobility, tunable bandgap and highly anisotropic properties, but it is chemically reactive and degrades rapidly in ambient conditions. Here we show that covalent aryl diazonium functionalization suppresses the chemical degradation of exfoliated BP even after three weeks of ambient exposure. This chemical modification scheme spontaneously forms phosphorus-carbon bonds, has a reaction rate sensitive to the aryl diazonium substituent and alters the electronic properties of exfoliated BP, ultimately yielding a strong, tunable p-type doping that simultaneously improves the field-effect transistor mobility and on/off current ratio. This chemical functionalization pathway controllably modifies the properties of exfoliated BP, and thus improves its prospects for nanoelectronic applications.

Chemically Tailoring Semiconducting Two-Dimensional Transition Metal Dichalcogenides and Black Phosphorus

Two-dimensional (2D) semiconducting transition metal dichalcogenides (TMDCs) and black phosphorus (BP) have beneficial electronic, optical, and physical properties at the few-layer limit. As atomically thin materials, 2D TMDCs and BP are highly sensitive to their environment and chemical modification, resulting in a strong dependence of their properties on substrate effects, intrinsic defects, and extrinsic adsorbates. Furthermore, the integration of 2D semiconductors into electronic and optoelectronic devices introduces unique challenges at metal-semiconductor and dielectric-semiconductor interfaces. Here, we review emerging efforts to understand and exploit chemical effects to influence the properties of 2D TMDCs and BP. In some cases, surface chemistry leads to significant degradation, thus necessitating the development of robust passivation schemes. On the other hand, appropriately designed chemical modification can be used to beneficially tailor electronic properties, such as controlling doping levels and charge carrier concentrations. Overall, chemical methods allow substantial tunability of the properties of 2D TMDCs and BP, thereby enabling significant future opportunities to optimize performance for device applications.

Anisotropic Thermal Conductivity of Exfoliated Black Phosphorus.

The anisotropic thermal conductivity of passivated black phosphorus (BP), a reactive two-dimensional material with strong in-plane anisotropy, is ascertained. The room-temperature thermal conductivity for three crystalline axes of exfoliated BP is measured by time-domain thermo-reflectance. The thermal conductivity along the zigzag direction is ≈2.5 times higher than that of the armchair direction.

Stable aqueous dispersions of optically and electronically active phosphorene.

Significance Few-layered phosphorene, which is isolated through exfoliation from black phosphorus, has attracted great interest due to its unique electronic and optical properties. Although solution-based exfoliation methods have been developed for black phosphorus, these techniques have thus far used anhydrous organic solvents. This approach minimizes exposure to known oxidizing species, but at the cost of limited exfoliation yield and relatively thick flakes. Here, we overcome these limitations by using stabilizing surfactants in deoxygenated water, which results in phosphorene down to the monolayer limit. The resulting aqueous phosphorene dispersions show layer-dependent photoluminescence and enable high-performance field-effect transistors. Overall, this approach holds promise for the solution-phase production of few-layered phosphorene in emerging large-volume applications including electronics and optoelectronics. Understanding and exploiting the remarkable optical and electronic properties of phosphorene require mass production methods that avoid chemical degradation. Although solution-based strategies have been developed for scalable exfoliation of black phosphorus, these techniques have thus far used anhydrous organic solvents in an effort to minimize exposure to known oxidants, but at the cost of limited exfoliation yield and flake size distribution. Here, we present an alternative phosphorene production method based on surfactant-assisted exfoliation and postprocessing of black phosphorus in deoxygenated water. From comprehensive microscopic and spectroscopic analysis, this approach is shown to yield phosphorene dispersions that are stable, highly concentrated, and comparable to micromechanically exfoliated phosphorene in structure and chemistry. Due to the high exfoliation efficiency of this process, the resulting phosphorene flakes are thinner than anhydrous organic solvent dispersions, thus allowing the observation of layer-dependent photoluminescence down to the monolayer limit. Furthermore, to demonstrate preservation of electronic properties following solution processing, the aqueous-exfoliated phosphorene flakes are used in field-effect transistors with high drive currents and current modulation ratios. Overall, this method enables the isolation and mass production of few-layer phosphorene, which will accelerate ongoing efforts to realize a diverse range of phosphorene-based applications.

Probing Out-of-Plane Charge Transport in Black Phosphorus with Graphene-Contacted Vertical Field-Effect Transistors

Black phosphorus (BP) has recently emerged as a promising narrow band gap layered semiconductor with optoelectronic properties that bridge the gap between semimetallic graphene and wide band gap transition metal dichalcogenides such as MoS2. To date, BP field-effect transistors have utilized a lateral geometry with in-plane transport dominating device characteristics. In contrast, we present here a vertical field-effect transistor geometry based on a graphene/BP van der Waals heterostructure. The resulting device characteristics include high on-state current densities (>1600 A/cm(2)) and current on/off ratios exceeding 800 at low temperature. Two distinct charge transport mechanisms are identified, which are dominant for different regimes of temperature and gate voltage. In particular, the Schottky barrier between graphene and BP determines charge transport at high temperatures and positive gate voltages, whereas tunneling dominates at low temperatures and negative gate voltages. These results elucidate out-of-plane electronic transport in BP and thus have implications for the design and operation of BP-based van der Waals heterostructures.

Metal Oxide Nanoparticle Growth on Graphene via Chemical Activation with Atomic Oxygen

Chemically interfacing the inert basal plane of graphene with other materials has limited the development of graphene-based catalysts, composite materials, and devices. Here, we overcome this limitation by chemically activating epitaxial graphene on SiC(0001) using atomic oxygen. Atomic oxygen produces epoxide groups on graphene, which act as reactive nucleation sites for zinc oxide nanoparticle growth using the atomic layer deposition precursor diethyl zinc. In particular, exposure of epoxidized graphene to diethyl zinc abstracts oxygen, creating mobile species that diffuse on the surface to form metal oxide clusters. This mechanism is corroborated with a combination of scanning probe microscopy, Raman spectroscopy, and density functional theory and can likely be generalized to a wide variety of related surface reactions on graphene.

Rapid and Large-Area Characterization of Exfoliated Black Phosphorus Using Third-Harmonic Generation Microscopy

Black phosphorus (BP) is a layered semiconductor that recently has been the subject of intense research due to its novel electrical and optical properties, which compare favorably to those of graphene and the transition metal dichalcogenides. In particular, BP has a direct bandgap that is thickness-dependent and highly anisotropic, making BP an interesting material for nanoscale optical and optoelectronic applications. Here, we present a study of the anisotropic third-harmonic generation (THG) in exfoliated BP using a fast scanning multiphoton characterization method. We find that the anisotropic THG arises directly from the crystal structure of BP. We calculate the effective third-order susceptibility of BP to be ∼1.64 × 10-19 m2 V-2. Further, we demonstrate that multiphoton microscopy can be used for rapid, large-area characterization indexing of the crystallographic orientations of many exfoliated BP flakes from one set of multiphoton images. This method is therefore beneficial for samples of areas ∼1 cm2 in future investigations of the properties and growth of BP.

3D Anisotropic Thermal Conductivity of Exfoliated Rhenium Disulfide

ReS2 represents a different class of 2D materials, which is characterized by low symmetry having 1D metallic chains within the planes and extremely weak interlayer bonding. Here, the thermal conductivity of single-crystalline ReS2 in a distorted 1T phase is determined at room temperature for the in-plane directions parallel and perpendicular to the Re-chains, and the through-plane direction using time-domain thermoreflectance. ReS2 is prepared in the form of flakes having thicknesses of 60-450 nm by micromechanical exfoliation, and their crystalline orientations are identified by polarized Raman spectroscopy. The in-plane thermal conductivity is higher along the Re-chains, (70 ± 18) W m-1 K-1 , as compared to transverse to the chains, (50 ± 13) W m-1 K-1 . As expected from the weak interlayer bonding, the through-plane thermal conductivity is the lowest observed to date for 2D materials, (0.55 ± 0.07) W m-1 K-1 , resulting in a remarkably high anisotropy of (130 ± 40) and (90 ± 30) for the two in-plane directions. The thermal conductivity and interface thermal conductance of ReS2 are discussed relative to the other 2D materials.

All-Electrical Determination of Crystal Orientation in Anisotropic Two-Dimensional Materials

The crystal orientation of an exfoliated black phosphorous flake is determined by purely electrical means. A sequence of three resistance measurements on an arbitrarily shaped flake with five contacts determines the three independent components of the anisotropic in-plane resistivity tensor, thereby revealing the crystal axes. The resistivity anisotropy ratio decreases linearly with increasing temperature T and carrier density reaching a maximum ratio of 3.0 at low temperatures and densities, while mobility indicates impurity scattering at low T and acoustic phonon scattering at high T.