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I. V. Grigorieva

Publications and source records attributed to I. V. Grigorieva.

At least 55 records · Page 3Linked to original sources
arXiv2014

Square ice in graphene nanocapillaries

Adsorbed layers of water are ubiquitously present at surfaces and fill in microscopic pores, playing a central role in many phenomena in such diverse fields as materials science, geology, biology, tribology, nanotechnology. Despite such importance, the crystal structure of nanoconfined water remains largely unknown. Here we report high-resolution electron microscopy of mono- and few- layers of water confined between two graphene sheets, an archetypal example of hydrophobic confinement. Confined water is found to form square ice at room temperature - a phase with symmetry principally different from the conventional tetrahedral geometry of hydrogen bonding. The square ice has a high packing density with a lattice constant of 2.83 angstrom and during TEM observation assembles in bi- and tri- layer crystallites exhibiting AA stacking. Our findings are important for understanding of interfacial phenomena and, in particular, shed light on ultrafast transport of water through hydrophobic nanocapillaries. Our MD simulations show that square ice is likely to be common inside hydrophobic nanochannels, independent of their exact atomic makeup.

cond-mat.mes-hall↗
arXiv2014

Proton transport through one atom thick crystals

Graphene is impermeable to all gases and liquids, and even such a small atom as hydrogen is not expected to penetrate through graphene's dense electronic cloud within billions of years. Here we show that monolayers of graphene and hexagonal boron nitride (hBN) are unexpectedly permeable to thermal protons, hydrogen ions under ambient conditions. As a reference, no proton transport could be detected for a monolayer of molybdenum disulfide, bilayer graphene or multilayer hBN. At room temperature, monolayer hBN exhibits the highest proton conductivity with a low activation energy of about 0.3 eV but graphene becomes a better conductor at elevated temperatures such that its resistivity to proton flow is estimated to fall below 10^-3 Ohm per cm2 above 250 C. The proton barriers can be further reduced by decorating monolayers with catalytic nanoparticles. These atomically thin proton conductors could be of interest for many hydrogen-based technologies.

cond-mat.mtrl-sci↗
arXiv2014

Detecting Topological Currents in Graphene Superlattices

Topological materials may exhibit Hall-like currents flowing transversely to the applied electric field even in the absence of a magnetic field. In graphene superlattices, which have broken inversion symmetry, topological currents originating from graphene's two valleys are predicted to flow in opposite directions and combine to produce long-range charge neutral flow. We observe this effect as a nonlocal voltage at zero magnetic field in a narrow energy range near Dirac points at distances as large as several microns away from the nominal current path. Locally, topological currents are comparable in strength to the applied current, indicating large valley-Hall angles. The long-range character of topological currents and their transistor-like control by gate voltage can be exploited for information processing based on the valley degrees of freedom.

cond-mat.mes-hall↗
arXiv2014

Hierarchy of Hofstadter states and replica quantum Hall ferromagnetism in graphene superlattices

Self-similarity and fractals have fascinated researchers across various disciplines. In graphene placed on boron nitride and subjected to a magnetic field, self-similarity appears in the form of numerous replicas of the original Dirac spectrum, and their quantization gives rise to a fractal pattern of Landau levels, referred to as the Hofstadter butterfly. Here we employ capacitance spectroscopy to probe directly the density of states (DoS) and energy gaps in this spectrum. Without a magnetic field, replica spectra are seen as pronounced DoS minima surrounded by van Hove singularities. The Hofstadter butterfly shows up as recurring Landau fan diagrams in high fields. Electron-electron interactions add another twist to the self-similar behaviour. We observe suppression of quantum Hall ferromagnetism, a reverse Stoner transition at commensurable fluxes and additional ferromagnetism within replica spectra. The strength and variety of the interaction effects indicate a large playground to study many-body physics in fractal Dirac systems.

cond-mat.mes-hall↗
arXiv2014

Precise and ultrafast molecular sieving through graphene oxide membranes

There has been intense interest in filtration and separation properties of graphene-based materials that can have well-defined nanometer pores and exhibit low frictional water flow inside them. Here we investigate molecular permeation through graphene oxide laminates. They are vacuum-tight in the dry state but, if immersed in water, act as molecular sieves blocking all solutes with hydrated radii larger than 4.5A. Smaller ions permeate through the membranes with little impedance, many orders of magnitude faster than the diffusion mechanism can account for. We explain this behavior by a network of nanocapillaries that open up in the hydrated state and accept only species that fit in. The ultrafast separation of small salts is attributed to an 'ion sponge' effect that results in highly concentrated salt solutions inside graphene capillaries.

cond-mat.mtrl-sci↗
arXiv2013

Van der Waals heterostructures

Research on graphene and other two-dimensional atomic crystals is intense and likely to remain one of the hottest topics in condensed matter physics and materials science for many years. Looking beyond this field, isolated atomic planes can also be reassembled into designer heterostructures made layer by layer in a precisely chosen sequence. The first - already remarkably complex - such heterostructures (referred to as 'van der Waals') have recently been fabricated and investigated revealing unusual properties and new phenomena. Here we review this emerging research area and attempt to identify future directions. With steady improvement in fabrication techniques, van der Waals heterostructures promise a new gold rush, rather than a graphene aftershock.

cond-mat.mtrl-sci↗
arXiv2013

Dual origin of defect magnetism in graphene and its reversible switching by molecular doping

A possibility to control magnetic properties by using electric fields is one of the most desirable characteristics for spintronics applications. Finding a suitable material remains an elusive goal, with only a few candidates found so far. Graphene is one of them and offers a hope due to its weak spin-orbit interaction, the ability to control electronic properties by the electric field effect and the possibility to introduce paramagnetic centres such as vacancies and adatoms. Here we show that adatoms magnetism in graphene is itinerant and can be controlled by doping, so that magnetic moments can be switched on and off. The much-discussed vacancy magnetism is found to have a dual origin, with two approximately equal contributions: one coming from the same itinerant magnetism and the other due to broken bonds. Our work suggests that magnetic response of graphene can be controlled by the field effect, similar to its transport and optical properties, and that spin diffusion length can be significantly enhanced above a certain carrier density.

cond-mat.mes-hall↗
arXiv2013

Cloning of Dirac fermions in graphene superlattices

Lateral superlattices have attracted major interest as this may allow one to modify spectra of two dimensional electron systems and, ultimately, create materials with tailored electronic properties. Previously, it proved difficult to realize superlattices with sufficiently short periodicity and weak disorder, and most of the observed features could be explained in terms of commensurate cyclotron orbits. Evidence for the formation of superlattice minibands (so called Hofstadter's butterfly) has been limited to the observation of new low-field oscillations and an internal structure within Landau levels. Here we report transport properties of graphene placed on a boron nitride substrate and accurately aligned along its crystallographic directions. The substrate's moire potential leads to profound changes in graphene's electronic spectrum. Second-generation Dirac points appear as pronounced peaks in resistivity accompanied by reversal of the Hall effect. The latter indicates that the sign of the effective mass changes within graphene's conduction and valence bands. Quantizing magnetic fields lead to Zak-type cloning of the third generation of Dirac points that are observed as numerous neutrality points in fields where a unit fraction of the flux quantum pierces the superlattice unit cell. Graphene superlattices open a venue to study the rich physics expected for incommensurable quantum systems and illustrate the possibility to controllably modify electronic spectra of 2D atomic crystals by using their crystallographic alignment within van der Waals heterostuctures.

cond-mat.mes-hall↗
arXiv2012

Strong Coulomb drag and broken symmetry in double-layer graphene

Spatially separated electron systems remain strongly coupled by electron-electron interactions even when they cannot exchange particles, provided that the layer separation d is comparable to a characteristic distance l between charge carriers within layers. One of the consequences of this remote coupling is a phenomenon called Coulomb drag, in which an electric current passed through one of the layers causes frictional charge flow in the other layer. Previously, only the regime of weak (d>>l) to intermediate (d ~ l) coupling could be studied experimentally. Here we use graphene-BN heterostructures with d down to 1 nm to probe interlayer interactions and Coulomb drag in the limit d<<l where the two Dirac liquids effectively nest within the same plane, but still can be tuned and measured independently. The strongly interacting regime reveals many unpredicted features that are qualitatively different from those observed previously. In particular, although drag vanishes because of electron-hole symmetry when either layer is neutral, we find that drag is at its strongest when /both/ layers are neutral. Under this circumstance, drag is positive in zero magnetic field but changes its sign and rapidly grows in strength with field. The drag remains strong at room temperature. The broken electron-hole symmetry is attributed to mutual polarization of closely-spaced interacting layers. The two-fluid Dirac system offers a large parameter space for further investigation of strong interlayer interaction phenomena.

cond-mat.mes-hall↗
arXiv2012

Revealing common artifacts due to ferromagnetic inclusions in highly-oriented pyrolytic graphite

We report on an extensive investigation to figure out the origin of room-temperature ferromagnetism that is commonly observed by SQUID magnetometry in highly-oriented pyrolytic graphite (HOPG). Electron backscattering and X-ray microanalysis revealed the presence of micron-size magnetic clusters (predominantly Fe) that are rare and would be difficult to detect without careful search in a scanning electron microscope in the backscattering mode. The clusters pin to crystal boundaries and their quantities match the amplitude of typical ferromagnetic signals. No ferromagnetic response is detected in samples where we could not find such magnetic inclusions. Our experiments show that the frequently reported ferromagnetism in pristine HOPG is most likely to originate from contamination with Fe-rich inclusions introduced presumably during crystal growth.

cond-mat.mtrl-sci↗
arXiv2012

Spin-half paramagnetism in graphene induced by point defects

Using magnetization measurements, we show that point defects in graphene - fluorine adatoms and irradiation defects (vacancies) - carry magnetic moments with spin 1/2. Both types of defects lead to notable paramagnetism but no magnetic ordering could be detected down to liquid helium temperatures. The induced paramagnetism dominates graphene's low-temperature magnetic properties despite the fact that maximum response we could achieve was limited to one moment per approximately 1000 carbon atoms. This limitation is explained by clustering of adatoms and, for the case of vacancies, by losing graphene's structural stability.

cond-mat.mes-hall↗
arXiv2011

Unimpeded permeation of water through helium-leak-tight graphene-based membranes

Permeation through nanometer pores is important in the design of materials for filtration and separation techniques and because of unusual fundamental behavior arising at the molecular scale. We found that submicron-thick membranes made from graphene oxide can be completely impermeable to liquids, vapors and gases, including helium, but allow unimpeded permeation of water (H2O permeates through the membranes at least 10^10 times faster than He). We attribute these seemingly incompatible observations to a low-friction flow of a monolayer of water through two dimensional capillaries formed by closely spaced graphene sheets. Diffusion of other molecules is blocked by reversible narrowing of the capillaries in low humidity and/or by their clogging with water.

cond-mat.mtrl-sci↗
arXiv2011

Dirac cones reshaped by interaction effects in suspended graphene

We report measurements of the cyclotron mass in graphene for carrier concentrations n varying over three orders of magnitude. In contrast to the single-particle picture, the real spectrum of graphene is profoundly nonlinear so that the Fermi velocity describing the spectral slope reaches ~3x10^6 m/s at n <10^10 cm^-2, three times the value commonly used for graphene. The observed changes are attributed to electron-electron interaction that renormalizes the Dirac spectrum because of weak screening. Our experiments also put an upper limit of ~0.1 meV on the possible gap in graphene.

cond-mat.mes-hall↗
arXiv2010

Limits on intrinsic magnetism in graphene

We have studied magnetization of graphene nanocrystals obtained by sonic exfoliation of graphite. No ferromagnetism is detected at any temperature down to 2 K. Neither do we find strong paramagnetism expected due to the massive amount of edge defects. Rather, graphene is strongly diamagnetic, similar to graphite. Our nanocrystals exhibit only a weak paramagnetic contribution noticeable below 50K. The measurements yield a single species of defects responsible for the paramagnetism, with approximately one magnetic moment per typical graphene crystallite.

cond-mat.mes-hall↗
arXiv2010

Fluorographene: Two Dimensional Counterpart of Teflon

We report a stoichiometric derivative of graphene with a fluorine atom attached to each carbon. Raman, optical, structural, micromechanical and transport studies show that the material is qualitatively different from the known graphene-based nonstoichiometric derivatives. Fluorographene is a high-quality insulator (resistivity >10^12 Ohm per square) with an optical gap of 3 eV. It inherits the mechanical strength of graphene, exhibiting Young's modulus of 100 N/m and sustaining strains of 15%. Fluorographene is inert and stable up to 400C even in air, similar to Teflon.

cond-mat.mtrl-sci↗
arXiv2010

On resonant scatterers as a factor limiting carrier mobility in graphene

We show that graphene deposited on a substrate has a non-negligible density of atomic scale defects. This is evidenced by a previously unnoticed D peak in the Raman spectra with intensity of about 1% with respect to the G peak. We evaluated the effect of such impurities on electron transport by mimicking them with hydrogen adsorbates and measuring the induced changes in both mobility and Raman intensity. If the intervalley scatterers responsible for the D peak are monovalent, their concentration is sufficient to account for the limited mobilities achievable in graphene on a substrate.

cond-mat.mes-hall↗
arXiv2009

Influence of metal contacts and charge inhomogeneity on transport properties of graphene near the neutrality point

There is an increasing amount of literature concerning electronic properties of graphene close to the neutrality point. Many experiments continue using the two-probe geometry or invasive contacts or do not control samples' macroscopic homogeneity. We believe that it is helpful to point out some problems related to such measurements. By using experimental examples, we illustrate that the charge inhomogeneity induced by spurious chemical doping or metal contacts can lead to large systematic errors in assessing graphene's transport properties and, in particular, its minimal conductivity. The problems are most severe in the case of two-probe measurements where the contact resistance is found to strongly vary as a function of gate voltage.

cond-mat.mes-hall↗