Ekaterina Khestanova

Quality Heterostructures from Two-Dimensional Crystals Unstable in Air by Their Assembly in Inert Atmosphere

Many layered materials can be cleaved down to individual atomic planes, similar to graphene, but only a small minority of them are stable under ambient conditions. The rest react and decompose in air, which has severely hindered their investigation and potential applications. Here we introduce a remedial approach based on cleavage, transfer, alignment, and encapsulation of air-sensitive crystals, all inside a controlled inert atmosphere. To illustrate the technology, we choose two archetypal two-dimensional crystals that are of intense scientific interest but are unstable in air: black phosphorus and niobium diselenide. Our field-effect devices made from their monolayers are conductive and fully stable under ambient conditions, which is in contrast to the counterparts processed in air. NbSe2 remains superconducting down to the monolayer thickness. Starting with a trilayer, phosphorene devices reach sufficiently high mobilities to exhibit Landau quantization. The approach offers a venue to significantly expand the range of experimentally accessible two-dimensional crystals and their heterostructures.

Negative local resistance caused by viscous electron backflow in graphene

Electrons that flow like a fluid Electrons inside a conductor are often described as flowing in response to an electric field. This flow rarely resembles anything like the familiar flow of water through a pipe, but three groups describe counterexamples (see the Perspective by Zaanen). Moll et al. found that the viscosity of the electron fluid in thin wires of PdCoO2 had a major effect on the flow, much like what happens in regular fluids. Bandurin et al. found evidence in graphene of electron whirlpools similar to those formed by viscous fluid flowing through a small opening. Finally, Crossno et al. observed a huge increase of thermal transport in graphene, a signature of so-called Dirac fluids. Science, this issue p. 1061, 1055, 1058; see also p. 1026 Proximity transport measurements find evidence of whirlpools of graphene’s viscous electronic fluid. [Also see Perspective by Zaanen] Graphene hosts a unique electron system in which electron-phonon scattering is extremely weak but electron-electron collisions are sufficiently frequent to provide local equilibrium above the temperature of liquid nitrogen. Under these conditions, electrons can behave as a viscous liquid and exhibit hydrodynamic phenomena similar to classical liquids. Here we report strong evidence for this transport regime. We found that doped graphene exhibits an anomalous (negative) voltage drop near current-injection contacts, which is attributed to the formation of submicrometer-size whirlpools in the electron flow. The viscosity of graphene’s electron liquid is found to be ~0.1 square meters per second, an order of magnitude higher than that of honey, in agreement with many-body theory. Our work demonstrates the possibility of studying electron hydrodynamics using high-quality graphene.

Universal shape and pressure inside bubbles appearing in van der Waals heterostructures

Trapped substances between a two-dimensional (2D) crystal and an atomically flat substrate lead to the formation of bubbles. Their size, shape and internal pressure are determined by the competition between van der Waals attraction of the crystal to the substrate and the elastic energy needed to deform it, allowing to use bubbles to study elastic properties of 2D crystals and conditions of confinement. Using atomic force microscopy, we analysed a variety of bubbles formed by monolayers of graphene, boron nitride and MoS2. Their shapes are found to exhibit universal scaling, in agreement with our analysis based on the theory of elasticity of membranes. We also measured the hydrostatic pressure induced by the confinement, which was found to reach tens of MPa inside submicron bubbles. This agrees with our theory estimates and suggests that for even smaller, sub-10 nm bubbles the pressure can be close to 1 GPa and may modify properties of a trapped material.Trapped substances between a 2D crystal, such as graphene, and an atomically flat substrate, for example, hexagonal boron nitride, give rise to the formation of bubbles. We show that the size, shape and internal pressure inside these bubbles are determined by the competition between van der Waals attraction of a 2D crystal to the substrate and the elastic energy needed to deform the atomically thin layer. This presents opportunities to use bubbles to study the elasticity of 2D materials as well as the conditions of confinement, yet none of these have been explored so far, either theoretically or experimentally. We have created a variety of bubbles formed by monolayers of graphene, hBN and MoS2 mechanically exfoliated onto hBN, graphite and MoS2 substrates. Their shapes, analyzed using atomic force microscopy, are found to exhibit universal scaling with well-defined aspect ratios, in agreement with theoretical analysis based on general properties of membranes. We also measured the pressure induced by the confinement, which increased with decreasing bubble’s size and reached tens on MPa inside submicron bubbles. This agrees with our theory estimates and suggests that for bubbles with radii . 10 nm hydrostatic pressures can reach close to 1 GPa, which may modify the properties of a trapped material.

Total Ionizing Dose Effects on hBN Encapsulated Graphene Devices

The constant-voltage electrical stress and 10-keV X-ray irradiation responses of encapsulated graphene-hBN devices are evaluated. Both constant-voltage stress and X-ray exposure induce only modest shifts in the current and the Dirac point of the graphene. Charge trapping at or near the graphene/BN interface is observed after X-ray irradiation. The experimental results suggest that net hole trapping occurs in the BN at low doses and that net electron trapping occurs at higher doses. First-principles calculations also demonstrate that hydrogenated substitutional carbon impurities at B/N sites at or near the graphene/BN interface can play an additional role in the radiation response of these structures.

High-temperature quantum oscillations caused by recurring Bloch states in graphene superlattices

Heat-loving quantum oscillations The shape of the Fermi surface in a conductor can be gleaned through quantum oscillations—periodic changes in transport properties as an external magnetic field is varied. Like most quantum properties, the phenomenon can usually be observed only at very low temperatures. Krishna Kumar et al. report quantum oscillations in graphene that do not go away even at the temperature of boiling water. Although “ordinary,” low-temperature quantum oscillations die away, another oscillatory behavior sets in that is extremely robust to heating. These resilient oscillations appear only in samples in which graphene is nearly aligned with its hexagonal boron nitride substrate, indicating that they are caused by the potential of the moiré superlattice that forms in such circumstances. Science, this issue p. 181 Magnetotransport in graphene–hexagonal boron nitride heterostructures exhibits robust oscillations. Cyclotron motion of charge carriers in metals and semiconductors leads to Landau quantization and magneto-oscillatory behavior in their properties. Cryogenic temperatures are usually required to observe these oscillations. We show that graphene superlattices support a different type of quantum oscillation that does not rely on Landau quantization. The oscillations are extremely robust and persist well above room temperature in magnetic fields of only a few tesla. We attribute this phenomenon to repetitive changes in the electronic structure of superlattices such that charge carriers experience effectively no magnetic field at simple fractions of the flux quantum per superlattice unit cell. Our work hints at unexplored physics in Hofstadter butterfly systems at high temperatures.

Atomic Defects and Doping of Monolayer NbSe2

We have investigated the structure of atomic defects within monolayer NbSe2 encapsulated in graphene by combining atomic resolution transmission electron microscope imaging, density functional theory (DFT) calculations, and strain mapping using geometric phase analysis. We demonstrate the presence of stable Nb and Se monovacancies in monolayer material and reveal that Se monovacancies are the most frequently observed defects, consistent with DFT calculations of their formation energy. We reveal that adventitious impurities of C, N, and O can substitute into the NbSe2 lattice stabilizing Se divacancies. We further observe evidence of Pt substitution into both Se and Nb vacancy sites. This knowledge of the character and relative frequency of different atomic defects provides the potential to better understand and control the unusual electronic and magnetic properties of this exciting two-dimensional material.

Unusual Suppression of the Superconducting Energy Gap and Critical Temperature in Atomically Thin NbSe2

It is well-known that superconductivity in thin films is generally suppressed with decreasing thickness. This suppression is normally governed by either disorder-induced localization of Cooper pairs, weakening of Coulomb screening, or generation and unbinding of vortex-antivortex pairs as described by the Berezinskii-Kosterlitz-Thouless (BKT) theory. Defying general expectations, few-layer NbSe2, an archetypal example of ultrathin superconductors, has been found to remain superconducting down to monolayer thickness. Here, we report measurements of both the superconducting energy gap Δ and critical temperature TC in high-quality monocrystals of few-layer NbSe2, using planar-junction tunneling spectroscopy and lateral transport. We observe a fully developed gap that rapidly reduces for devices with the number of layers N ≤ 5, as does their TC. We show that the observed reduction cannot be explained by disorder, and the BKT mechanism is also excluded by measuring its transition temperature that for all N remains very close to TC. We attribute the observed behavior to changes in the electronic band structure predicted for mono- and bi- layer NbSe2 combined with inevitable suppression of the Cooper pair density at the superconductor-vacuum interface. Our experimental results for N > 2 are in good agreement with the dependences of Δ and TC expected in the latter case while the effect of band-structure reconstruction is evidenced by a stronger suppression of Δ and the disappearance of its anisotropy for N = 2. The spatial scale involved in the surface suppression of the density of states is only a few angstroms but cannot be ignored for atomically thin superconductors.

Magnetotransport in single-layer graphene in a large parallel magnetic field

Graphene on hexagonal boron-nitride (h-BN) is an atomically flat conducting system that is ideally suited for probing the effect of Zeeman splitting on electron transport. We demonstrate by magneto-transport measurements that a parallel magnetic field up to 30 Tesla does not affect the transport properties of graphene on h-BN even at charge neutrality where such an effect is expected to be maximal. The only magnetoresistance detected at low carrier concentrations is shown to be associated with a small perpendicular component of the field which cannot be fully eliminated in the experiment. Despite the high mobility of charge carries at low temperatures, we argue that the effects of Zeeman splitting are fully masked by electrostatic potential fluctuations at charge neutrality.