Large-Area Single-Crystal Graphene via Self-Organization at the Macroscale.

In 1665 Christiaan Huygens first noticed how two pendulums, regardless of their initial state, would synchronize.  It is now known that the universe is full of complex self-organizing systems, from neural networks to correlated materials. Here, graphene flakes, nucleated over a polycrystalline graphene film, synchronize during growth so as to ultimately yield a common crystal orientation at the macroscale. Strain and diffusion gradients are argued as the probable causes for the long-range cross-talk between flakes and the formation of a single-grain graphene layer. The work demonstrates that graphene synthesis can be advanced to control the nucleated crystal shape, registry, and relative alignment between graphene crystals for large area, that is, a single-crystal bilayer, and (AB-stacked) few-layer graphene can been grown at the wafer scale.

Visualizing Poiseuille flow of hydrodynamic electrons.

Hydrodynamics, which generally describes the flow of a fluid, is expected to hold even for fundamental particles such as electrons when inter-particle interactions dominate1. Although various aspects of electron hydrodynamics have been revealed in recent experiments2-11, the fundamental spatial structure of hydrodynamic electrons-the Poiseuille flow profile-has remained elusive. Here we provide direct imaging of the Poiseuille flow of an electronic fluid, as well as a visualization of its evolution from ballistic flow. Using a scanning carbon nanotube single-electron transistor12, we image the Hall voltage of electronic flow through channels of high-mobility graphene. We find that the profile of the Hall field across the channel is a key physical quantity for distinguishing ballistic from hydrodynamic flow. We image the transition from flat, ballistic field profiles at low temperatures into parabolic field profiles at elevated temperatures, which is the hallmark of Poiseuille flow. The curvature of the imaged profiles is qualitatively reproduced by Boltzmann calculations, which allow us to create a 'phase diagram' that characterizes the electron flow regimes. Our results provide direct confirmation of Poiseuille flow in the solid state, and enable exploration of the rich physics of interacting electrons in real space.

Determining the Fermi level by absorption quenching of monolayer graphene by charge transfer doping.

While optical properties of graphene in the visible region are solely defined by the frequency-independent fine structure constant, an onset of absorption has been observed in the infrared region due to Pauli blocking of interband transitions. Here, we report a complete absorption quenching in the infrared region by coating graphene with bis(trifluoromethanesulfonyl)amine (TFSA), an optically transparent p-type chemical dopant. The Fermi level downshift due to TFSA doping results in enhanced transmission in the infrared region proportional to the doping concentration. An absorption quenching onset method, developed in our work, to extract the Fermi level shift in pristine and doped graphene agrees with values extracted from Raman G-band and 2D-band shifts, Hall measurements and the binding energy shift observed in X-ray photo-electron spectroscopy. Performing simple UV-visible transmittance spectroscopy to obtain the absorption quenching onset of graphene also allows detection of environmental and substrate effects via Fermi level shift. Our method opens up the practical implementation of this unique phenomenon of graphene in future optoelectronic devices.

Stranski-Krastanov and Volmer-Weber CVD Growth Regimes To Control the Stacking Order in Bilayer Graphene.

Aside from unusual properties of monolayer graphene, bilayer has been shown to have even more interesting physics, in particular allowing bandgap opening with dual gating for proper interlayer symmetry. Such properties, promising for device applications, ignited significant interest in understanding and controlling the growth of bilayer graphene. Here we systematically investigate a broad set of flow rates and relative gas ratio of CH4 to H2 in atmospheric pressure chemical vapor deposition of multilayered graphene. Two very different growth windows are identified. For relatively high CH4 to H2 ratios, graphene growth is relatively rapid with an initial first full layer forming in seconds upon which new graphene flakes nucleate then grow on top of the first layer. The stacking of these flakes versus the initial graphene layer is mostly turbostratic. This growth mode can be likened to Stranski-Krastanov growth. With relatively low CH4 to H2 ratios, growth rates are reduced due to a lower carbon supply rate. In addition bi-, tri-, and few-layer flakes form directly over the Cu substrate as individual islands. Etching studies show that in this growth mode subsequent layers form beneath the first layer presumably through carbon radical intercalation. This growth mode is similar to that found with Volmer-Weber growth and was shown to produce highly oriented AB-stacked materials. These systematic studies provide new insight into bilayer graphene formation and define the synthetic range where gapped bilayer graphene can be reliably produced.

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.

Oxidation Effect in Octahedral Hafnium Disulfide Thin Film.

Atomically smooth van der Waals materials are structurally stable in a monolayer and a few layers but are susceptible to oxygen-rich environments. In particular, recently emerging materials such as black phosphorus and perovskite have revealed stronger environmental sensitivity than other two-dimensional layered materials, often obscuring the interesting intrinsic electronic and optical properties. Unleashing the true potential of these materials requires oxidation-free sample preparation that protects thin flakes from air exposure. Here, we fabricated few-layer hafnium disulfide (HfS2) field effect transistors (FETs) using an integrated vacuum cluster system and study their electronic properties and stability under ambient conditions. By performing all the device fabrication and characterization procedure under an oxygen- and moisture-free environment, we found that few-layer AA-stacking HfS2-FETs display excellent field effect responses (Ion/Ioff ≈ 10(7)) with reduced hysteresis compared to the FETs prepared under ambient conditions. Oxidation of HfS2 occurs uniformly over the entire area, increasing the film thickness by 250% at a prolonged oxidation time of >120 h, while defects on the surface are the preferential initial oxidation sites. We further demonstrated that the stability of the device in air is significantly improved by passivating FETs with BN in a vacuum cluster.

Misorientation-angle-dependent electrical transport across molybdenum disulfide grain boundaries.

Grain boundaries in monolayer transition metal dichalcogenides have unique atomic defect structures and band dispersion relations that depend on the inter-domain misorientation angle. Here, we explore misorientation angle-dependent electrical transport at grain boundaries in monolayer MoS2 by correlating the atomic defect structures of measured devices analysed with transmission electron microscopy and first-principles calculations. Transmission electron microscopy indicates that grain boundaries are primarily composed of 5-7 dislocation cores with periodicity and additional complex defects formed at high angles, obeying the classical low-angle theory for angles <22°. The inter-domain mobility is minimized for angles <9° and increases nonlinearly by two orders of magnitude before saturating at ∼ 16 cm(2) V(-1) s(-1) around misorientation angle ≈ 20°. This trend is explained via grain-boundary electrostatic barriers estimated from density functional calculations and experimental tunnelling barrier heights, which are ≈ 0.5 eV at low angles and ≈ 0.15 eV at high angles (≥ 20°).

High-performance n-type black phosphorus transistors with type control via thickness and contact-metal engineering.

Recent work has demonstrated excellent p-type field-effect switching in exfoliated black phosphorus, but type control has remained elusive. Here, we report unipolar n-type black phosphorus transistors with switching polarity control via contact-metal engineering and flake thickness, combined with oxygen and moisture-free fabrication. With aluminium contacts to black phosphorus, a unipolar to ambipolar transition occurs as flake thickness increases from 3 to 13 nm. The 13-nm aluminium-contacted flake displays graphene-like symmetric hole and electron mobilities up to 950 cm(2) V(-1) s(-1) at 300 K, while a 3 nm flake displays unipolar n-type switching with on/off ratios greater than 10(5) (10(7)) and electron mobility of 275 (630) cm(2) V(-1) s(-1) at 300 K (80 K). For palladium contacts, p-type behaviour dominates in thick flakes, while 2.5-7 nm flakes have symmetric ambipolar transport. These results demonstrate a leap in n-type performance and exemplify the logical switching capabilities of black phosphorus.

Observing grain boundaries in CVD-grown monolayer transition metal dichalcogenides.

Two-dimensional monolayer transition metal dichalcogenides (TMdCs), driven by graphene science, revisit optical and electronic properties, which are markedly different from bulk characteristics. These properties are easily modified due to accessibility of all the atoms viable to ambient gases, and therefore, there is no guarantee that impurities and defects such as vacancies, grain boundaries, and wrinkles behave as those of ideal bulk. On the other hand, this could be advantageous in engineering such defects. Here, we report a method of observing grain boundary distribution of monolayer TMdCs by a selective oxidation. This was implemented by exposing directly the TMdC layer grown on sapphire without transfer to ultraviolet light irradiation under moisture-rich conditions. The generated oxygen and hydroxyl radicals selectively functionalized defective grain boundaries in TMdCs to provoke morphological changes at the boundary, where the grain boundary distribution was observed by atomic force microscopy and scanning electron microscopy. This paves the way toward the investigation of transport properties engineered by defects and grain boundaries.

Thermionic field emission transport in carbon nanotube transistors.

With experimental and analytical analysis, we demonstrate a relationship between the metal contact work function and the electrical transport properties saturation current (Isat) and differential conductance (σsd=∂Isd/∂Vsd) in ambient exposed carbon nanotubes (CNT). A single chemical vapor deposition (CVD) grown 6 mm long semiconducting single-walled CNT is electrically contacted with a statistically significant number of Hf, Cr, Ti, Pd, and Au electrodes, respectively. The observed exponentially increasing relationship of Isat and σsd with metal contact work function is explained by a theoretical model derived from thermionic field emission. Statistical analysis and spread of the data suggest that the conduction variability in same CNT devices results from differences in local surface potential of the metal contact. Based on the theoretical model and methodology, an improved CNT-based gas sensing device layout is suggested. A method to experimentally determine gas-induced work function changes in metals is also examined.

Anomalous Schottky barriers and contact band-to-band tunneling in carbon nanotube transistors.

Devices incorporating nanoscale materials, particularly carbon nanotubes (CNTs), offer exceptional electrical performance. Absent, however, is an experimentally backed model explaining contact-metal work function, device layout, and environment effects. To fill the void, this report introduces a surface-inversion channel model based on low temperature and electrical measurements of a distinct single-walled semiconducting CNT contacted by Hf, Cr, Ti, and Pd electrodes. Anomalous barrier heights and metal-contact dependent band-to-band tunneling phenomena are utilized to show that, dependent upon contact work function and gate field, transport occurs either directly between the metal and CNT channel or indirectly via injection of carriers from the metal-covered CNT region to the CNT channel. The model is consistent with previously contradictory experimental results, and the methodology is simple enough to apply in other contact-dominant systems.