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Graphene is increasingly explored as a possible platform for developing novel separation technologies (1-19). This interest has arisen because it is a maximally thin membrane that, once perforated with atomic accuracy, may allow ultrafast and highly selective sieving of gases, liquids, dissolved ions and other species of interest (2,9-19). However, a perfect graphene monolayer is impermeable to all atoms and molecules under ambient conditions (1-7): even hydrogen, the smallest of atoms, is expected to take billions of years to penetrate graphene's dense electronic cloud (3-6). Only accelerated atoms possess the kinetic energy required to do this (20,21). The same behaviour might reasonably be expected in the case of other atomically thin crystals (22,23). Here we report transport and mass spectroscopy measurements which establish that monolayers of graphene and hexagonal boron nitride (hBN) are highly permeable to thermal protons under ambient conditions, whereas no proton transport is detected for thicker crystals such as monolayer molybdenum disulphide, bilayer graphene or multilayer hBN. Protons present an intermediate case between electrons (which can tunnel easily through atomically thin barriers (24)) and atoms, yet our measured transport rates are unexpectedly high (4,5) and raise fundamental questions about the details of the transport process. We see the highest room-temperature proton conductivity with monolayer hBN, for which we measure a resistivity to proton flow of about 10 ω [cm.sup.2] and a low activation energy of about 0.3 electronvolts. At higher temperatures, hBN is outperformed by graphene, the resistivity of which is estimated to fall below [10.sup.-3] ω [cm.sup.2] above 250 degrees Celsius. Proton transport can be further enhanced by decorating the graphene and hBN membranes with catalytic metal nanoparticles. The high, selective proton conductivity and stability make one-atomthick crystals promising candidates for use in many hydrogen-based technologies., We have investigated the possibility of proton transport through monocrystalline membranes made from mono- and few-layer graphene, hBN, and molybdenum disulphide (Mo[S.sub.2]). The two-dimensional (2D) crystals (22,23) were obtained by [...]

X-ray photoemission electron microscopy (X-PEEM) and atomic force microscopy (AFM) are used for examining the morphology and stoichiometry of a model iron oxide magnetic tunneling junction heterostructure. Fe3O4(111) islands and alpha-Fe2O3(0001) terraces are observed in X-PEEM data.

Obtaining an accurate profile of the spatial sensitivity of Hall cross structures is crucial if such devices are to be used to analyze the switching behavior of magnetic nanostructures and determine the switching field distribution of bit patterned media. Here, we have used the anomalous Hall effect to investigate the switching of patterned Co/Pt multilayer magnetic nanoislands, where the Hall cross has been integrated into the Pt seed layer. Using the anomalous Hall output voltage we have observed the magnetic switching of individual islands, allowing the spatial sensitivity across a Hall cross structure to be determined. The experimental results agree well with numerical simulation studies, using a three-dimensional finite element model, and with existing theoretical studies, where the spatial sensitivity of two-dimensional Hall cross structures have been found numerically. [ABSTRACT FROM AUTHOR]

A detailed characterization of magnetic oxide films is essential to enable their use in magnetoresistive devices since their properties depend critically on stoichiometry and structural order. Here, the composition and magnetic properties of ultrathin iron oxide films grown epitaxially on Al2O3(0001) have been characterized using x-ray magnetic circular dichroism XMCD and magnetoresistance (MR) measurements. The XMCD data show by comparison with theoretical calculations that we have successfully found growth conditions for well ordered epitaxial films with Fe3O4 stoichiometry. Nonstoichiometric films exhibit, in addition to a relative reduction in Fe2+ ions, a net transfer of Fe3+ from tetrahedral to octahedral sites. The in-plane MR for both these films is found to be 1% at room temperature in a field of 1 T even though the electrical conductivity differs by a factor of 5. [ABSTRACT FROM AUTHOR]

High resolution magnetic force microscopy with in situ applied field is used for determining the switching field distribution (SFD) and hysteresis loop of the islands. It is shown that the coercivity is reduced and the width of the SFD is increased for the smallest islands, suggesting that they would not be well suited to data storage applications.

The composition and magnetic properties of stoichiometric and nonstoichiometric ultrathin iron oxide films grown epitaxially on Al2O3(0001) is characterized. X-ray magnetic circular dichroism XMCD and magnetoresistance (MR) measurements are used for the study.

The magnetic properties of a Cu capped thin film of magnetite (Fe3O4) grown epitaxially on Pt(111) are investigated. The reduced magnetic ordering temperature due to the finite film thickness is the main cause for a reduced magnetic moment in the thin film.

E-beam lithography has been used to pattern a continuous Co/Pt multilayer film with perpendicular anisotropy into circular islands of various sizes down to 25 nm diameter on a 60 nm pitch. High resolution magnetic force microscopy with in situ applied field has been used to directly determine the switching field distribution (SFD) and hysteresis loop of the islands. For the smallest islands, the coercivity is reduced and the width of the SFD is increased, indicating that they would not be well suited to data storage applications. [ABSTRACT FROM AUTHOR]

We study optical properties of optomagnetic metamaterials consisting of regular arrays of single and double Au nanodots (nanopillars). Using a combination of data from variable angle spectroscopic ellipsometry, transmission, and reflection measurements, we identify localized plasmon resonances of gold nanodots and measure their dependence on dot size and substrate type. We demonstrate that arrays of Au nanopillars can support narrow collective plasmon resonances coupled to in-plane and out-of-plane localized plasmon resonances. The spectral positions of these plasmon modes are extracted from the angular dependence of the transmission and reflection spectra for two beam polarizations. We show that nanoarrays exhibit dramatically different optical response on conductive and nonconductive substrates and study its angular dependence. The optical response of nanoarrays is described well by coupled dipole approximation. The procedure for extracting optical constants of metamaterials based on ellipsometry is discussed and applied to our samples resulting in a calculated negative index of refraction for double-dot arrays at green light. [ABSTRACT FROM AUTHOR]

We study a hybrid graphene plasmonic device that consists of a gold nanostripe array combined with graphene. We have measured significant changes in the optical properties of the nanostripe array after the transfer of monolayer or bilayer graphene on the top of it. We suggest that this modification is partly due to the resistive coupling of localized plasmon resonances through the highly mobile electrons of the graphene layer. Our results open up new possibilities for designing active optical elements to exploit the high sensitivity of graphene carrier-density to bias voltage for ultra-fast light modulation. This is especially interesting as the plasmonic resonances of metal nanostructures can lie in the visible, NIR and UV; important areas for many applications. [ABSTRACT FROM AUTHOR]

The non-trivial behaviour of phase is crucial for many important physical phenomena, such as, for example, the Aharonov-Bohm effect and the Berry phase. By manipulating the phase of light one can create 'twisted' photons, vortex knots and dislocations which has led to the emergence of the field of singular optics relying on abrupt phase changes. Here we demonstrate the feasibility of singular visible-light nano-optics which exploits the benefits of both plasmonic field enhancement and the peculiarities of the phase of light. We show that properly designed plasmonic metamaterials exhibit topologically protected zero reflection yielding to sharp phase changes nearby, which can be employed to radically improve the sensitivity of detectors based on plasmon resonances. By using reversible hydrogenation of graphene and binding of streptavidin-biotin, we demonstrate an areal mass sensitivity at a level of fg mm−2 and detection of individual biomolecules, respectively. Our proof-of-concept results offer a route towards simple and scalable single-molecule label-free biosensing technologies. [ABSTRACT FROM AUTHOR]

The ultimate aim of any detection method is to achieve such a level of sensitivity that individual quanta of a measured entity can be resolved. In the case of chemical sensors, the quantum is one atom or molecule. Such resolution has so far been beyond the reach of any detection technique, including solid-state gas sensors hailed for their exceptional sensitivity. The fundamental reason limiting the resolution of such sensors is fluctuations due to thermal motion of charges and defects, which lead to intrinsic noise exceeding the sought-after signal from individual molecules, usually by many orders of magnitude. Here, we show that micrometre-size sensors made from graphene are capable of detecting individual events when a gas molecule attaches to or detaches from graphene’s surface. The adsorbed molecules change the local carrier concentration in graphene one by one electron, which leads to step-like changes in resistance. The achieved sensitivity is due to the fact that graphene is an exceptionally low-noise material electronically, which makes it a promising candidate not only for chemical detectors but also for other applications where local probes sensitive to external charge, magnetic field or mechanical strain are required. [ABSTRACT FROM AUTHOR]

There are two known distinct types of the integer quantum Hall effect. One is the conventional quantum Hall effect, characteristic of two-dimensional semiconductor systems, and the other is its relativistic counterpart observed in graphene, where charge carriers mimic Dirac fermions characterized by Berry’s phase π, which results in shifted positions of the Hall plateaus. Here we report a third type of the integer quantum Hall effect. Charge carriers in bilayer graphene have a parabolic energy spectrum but are chiral and show Berry’s phase 2π affecting their quantum dynamics. The Landau quantization of these fermions results in plateaus in Hall conductivity at standard integer positions, but the last (zero-level) plateau is missing. The zero-level anomaly is accompanied by metallic conductivity in the limit of low concentrations and high magnetic fields, in stark contrast to the conventional, insulating behaviour in this regime. The revealed chiral fermions have no known analogues and present an intriguing case for quantum-mechanical studies. [ABSTRACT FROM AUTHOR]

Alkali metal coadsorption systems represent a step along the pathway from simple model adsorbate overlayers to more technologically relevant real systems. However, such is their complexity that very few systems have been structurally determined. Here we present a surface X-ray diffraction investigation of one of these systems, Ni(100)-(3 × 3)-(Cs+O). Here a structural determination is particularly challenging due to the presence of three species in the surface layers and by the size of the unit cell. As a first step, anomalous scattering has been used to determine whether there is a contribution of the nickel substrate to the fractional order diffraction intensity. Measurements of the fractional order rods at 10 eV and 200 eV below the nickel K edge (8333 eV) were used to probe the nickel contribution to the fractional order rods. It was found that the intensity of the scattering was unchanged, indicating that the fractional order peaks are caused by scattering from the coadsorbates only. This shows that the nickel surface layers are not changed by the adsorption and thus sets a useful constraint on the number of possible structures. [ABSTRACT FROM AUTHOR]

Discusses the measurement of the absolute quantum yield for alkali halides and the spectral transmission for alkaline earth fluoride windows to find an optimized bandpass combination for a solid state ultraviolet photon detector for inverse photoemission. Photocathodes and windows; Preparation of photocathode films; Detector design.

An obstacle to the use of graphene as an alternative to silicon electronics has been the absence of an energy gap between its conduction and valence bands, which makes it difficult to achieve low power dissipation in the OFF state. We report a bipolar field-effect transistor that exploits the low density of states in graphene and its one-atomic-layer thickness. Our prototype devices are graphene heterostructures with atomically thin boron nitride or molybdenum disulfide acting as a vertical transport barrier. They exhibit room-temperature switching ratios of ≈50 and ≈10,000, respectively. Such devices have potential for high-frequency operation and large-scale integration. [ABSTRACT FROM AUTHOR]

Abstract: 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. [Copyright &y& Elsevier]

We report the use of soft X-ray resonant reflectivity at the Fe M2,3 edges to probe the magnetic circular dichroism of non-stoichiometric Fe3−δO4 thin films grown epitaxially on Al2O3. Photon energy scans of the magnetic dichroism display features that arise from the different Fe cation sites, with relative intensities that depend on the incident angle of the X-rays. Comparisons are made between the dichroism measured with this technique and X-ray magnetic circular dichroism calculated for the three Fe sites in magnetite. [Copyright &y& Elsevier]

Atomically thin black phosphorus (BP) has attracted considerable interest due to its unique properties, such as an infrared band gap that depends on the number of layers and excellent electronic transport characteristics. This material is known to be sensitive to light and oxygen and degrades in air unless protected with an encapsulation barrier, limiting its exploitation in electrical devices. We present a new scalable technique for nanopatterning few layered BP by direct electron beam exposure of encapsulated crystals, achieving a spatial resolution down to 6 nm. By encapsulating the BP with single layer graphene or hexagonal boron nitride (hBN), we show that a focused electron probe can be used to produce controllable local oxidation of BP through nanometre size defects created in the encapsulation layer by the electron impact. We have tested the approach in the scanning transmission electron microscope (STEM) and using industry standard electron beam lithography (EBL). Etched regions of the BP are stabilized by a thin passivation layer and demonstrate typical insulating behavior as measured at 300 and 4.3 K. This new scalable approach to nanopatterning of thin air sensitive crystals has the potential to facilitate their wider use for a variety of sensing and electronics applications.

A new resist material for electron beam lithography has been created that is based on a supramolecular assembly. Initial studies revealed that with this supramolecular approach, high-resolution structures can be written that show unprecedented selectivity when exposed to etching conditions involving plasmas., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Plasmon-induced phenomena have recently attracted considerable attention. At the same time, relatively little research has been conducted on electrochemistry mediated by plasmon excitations. Here we report plasmon-induced formation of nanoscale quantized conductance filaments within metal-insulator-metal heterostructures. Plasmon-enhanced electromagnetic fields in an array of gold nanodots provide a straightforward means of forming conductive CrO x bridges across a thin native chromium oxide barrier between the nanodots and an underlying metallic Cr layer. The existence of these nanoscale conducting filaments is verified by transmission electron microscopy and contact resistance measurements. Their conductance was interrogated optically, revealing quantised relative transmission of light through the heterostructures across a wavelength range of 1-12 μm. Such plasmon-induced electrochemical processes open up new possibilities for the development of scalable devices governed by light.

Surface-enhanced Raman spectroscopy (SERS) enables sensitive chemical studies and materials identification, relying on electromagnetic (EM) and chemical-enhancement mechanisms. Here we introduce a tool for the correlative nanoimaging of EM and SERS hotspots, areas of strongly enhanced EM fields and Raman scattering, respectively. To that end, we implemented a grating spectrometer into a scattering-type scanning near-field optical microscope (s-SNOM) for mapping of both the elastically and inelastically (Raman) scattered light from the near-field probe, that is, a sharp silicon tip. With plasmon-resonant gold dimers (canonical SERS substrates) we demonstrate with nanoscale spatial resolution that the enhanced Raman scattering from the tip is strongly correlated with its enhanced elastic scattering, the latter providing access to the EM-field enhancement at the illumination frequency. Our technique has wide application potential in the correlative nanoimaging of local-field enhancement and SERS efficiency as well as in the investigation and quality control of novel SERS substrates.

We present our design, fabrication and characterization of resonance-controllable metamaterials operating at mid-infrared wavelengths. The metamaterials are composed of pairs of back-to-back or face-to-face U-shape split-ring resonators (SRRs). Transmission spectra of the metamaterials are measured using Fourier-transform infrared spectroscopy. The results show that the transmission resonance is dependent on the distance between the two SRRs in each SRR pair. The dips in the transmission spectrum shift to shorter wavelengths with increasing distance between the two SRRs for both the back-to-back and face-to-face SRR pairs. The position of the resonance dips in the spectrum can hence be controlled by the relative position of the SRRs. This mechanism of resonance control offers a promising way of developing metamaterials with tunability for optical filters and bio/chemical sensing devices in integrated nano-optics.

Capacitance measurements provide a powerful means of probing the density of states. The technique has proved particularly successful in studying 2D electron systems, revealing a number of interesting many-body effects. Here, we use large-area high-quality graphene capacitors to study behavior of the density of states in this material in zero and high magnetic fields. Clear renormalization of the linear spectrum due to electron-electron interactions is observed in zero field. Quantizing fields lead to splitting of the spin- and valley-degenerate Landau levels into quartets separated by interaction-enhanced energy gaps. These many-body states exhibit negative compressibility but the compressibility returns to positive in ultrahigh B. The reentrant behavior is attributed to a competition between field-enhanced interactions and nascent fractional states.

We characterize plasmonic enhancement in a hotspot between two Au nanodisks using Raman scattering of graphene. Single layer graphene is suspended across the dimer cavity and provides an ideal two-dimensional test material for the local near-field distribution. We detect a Raman enhancement of the order of 10(3) originating from the cavity. Spatially resolved Raman measurements reveal a near-field localization one order of magnitude smaller than the wavelength of the excitation, which can be turned off by rotating the polarization of the excitation. The suspended graphene is under tensile strain. The resulting phonon mode softening allows for a clear identification of the enhanced signal compared to unperturbed graphene.

We investigate the electronic properties of ultrathin hexagonal boron nitride (h-BN) crystalline layers with different conducting materials (graphite, graphene, and gold) on either side of the barrier layer. The tunnel current depends exponentially on the number of h-BN atomic layers, down to a monolayer thickness. Conductive atomic force microscopy scans across h-BN terraces of different thickness reveal a high level of uniformity in the tunnel current. Our results demonstrate that atomically thin h-BN acts as a defect-free dielectric with a high breakdown field. It offers great potential for applications in tunnel devices and in field-effect transistors with a high carrier density in the conducting channel., (© 2012 American Chemical Society)

Optics is renowned for displaying quantum phenomena. Indeed, studies of emission and absorption lines, the photoelectric effect and blackbody radiation helped to build the foundations of quantum mechanics. Nevertheless, it came as a surprise that the visible transparency of suspended graphene is determined solely by the fine structure constant, as this kind of universality had been previously reserved only for quantized resistance and flux quanta in superconductors. Here we describe a plasmonic system in which relative optical transparency is determined solely by the fine structure constant. The system consists of a regular array of gold nanoparticles fabricated on a thin metallic sublayer. We show that its relative transparency can be quantized in the near-infrared, which we attribute to the quantized contact resistance between the nanoparticles and the metallic sublayer. Our results open new possibilities in the exploration of universal dynamic conductance in plasmonic nanooptics.

A stoichiometric derivative of graphene with a fluorine atom attached to each carbon is reported. 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) Ω) with an optical gap of 3 eV. It inherits the mechanical strength of graphene, exhibiting a Young's modulus of 100 N m(-1) and sustaining strains of 15%. Fluorographene is inert and stable up to 400 °C even in air, similar to Teflon.

We present composite plasmonic nanostructures designed to achieve cascaded enhancement of electromagnetic fields at optical frequencies. Our structures were made with the help of electron-beam lithography and comprise a set of metallic nanodisks placed one above another. The optical properties of reproducible arrays of these structures were studied by using scanning confocal Raman spectroscopy. We show that our composite nanostructures robustly demonstrate dramatic enhancement of the Raman signals when compared to those measured from constituent elements.

Surface-enhanced Raman scattering (SERS) exploits surface plasmons induced by the incident field in metallic nanostructures to significantly increase the Raman intensity. Graphene provides the ideal prototype two-dimensional (2d) test material to investigate SERS. Its Raman spectrum is well-known, graphene samples are entirely reproducible, height controllable down to the atomic scale, and can be made virtually defect-free. We report SERS from graphene, by depositing arrays of Au particles of well-defined dimensions on a graphene/SiO(2) (300 nm)/Si system. We detect significant enhancements at 633 nm. To elucidate the physics of SERS, we develop a quantitative analytical and numerical theory. The 2d nature of graphene allows for a closed-form description of the Raman enhancement, in agreement with experiments. We show that this scales with the nanoparticle cross section, the fourth power of the Mie enhancement, and is inversely proportional to the tenth power of the separation between graphene and the center of the nanoparticle. One important consequence is that metallic nanodisks are an ideal embodiment for SERS in 2d.

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 ∼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 currently achievable in graphene on a substrate.

We study optical properties of optomagnetic metamaterials produced by regular arrays of double gold dots (nanopillars). Using combined data of spectroscopic ellipsometry, transmission and reflection measurements, we identify localized plasmon resonances of a nanopillar pair and measure their dependences on dot sizes. We formulate the necessary condition at which an effective field theory can be applied to describe optical properties of a composite medium and employ interferometry to measure phase shifts for our samples. A negative phase shift for transmitted green light coupled to an antisymmetric magnetic mode of a double-dot array is observed., ((c) 2010 Optical Society of America.)

We present results from composite plasmonic nanostructures designed to achieve the cascaded enhancement of electromagnetic fields at optical frequencies. Our structures comprise a small metallic nanodisc suspended above a larger disk. We probe the optical properties of these structures by coating them with a layer of a visible-light fluorophore and observing fluorescence signals with the help of scanning confocal microscopy. A 43 +/- 5-fold increase in the far-field fluorescence signal has been observed for two-tier composite nanostructures, when compared to the signal obtained from individual nanodiscs. Our results offer the prospect of using such nanostructures for field concentration, optical manipulation of nanoobjects, chemical and biological sensing.

An optical sensor for quantitative analysis of ultrathin films and adsorbed layers is described. Quantification of both layer thickness and refractive index (density) can be made for in situ and ex-situ coated films. With the use of two polarizations, in situ measurements are made via one path length in a young's interferometer arrangement while ex-situ measurements use multiple path lengths. The multiple path length young's interferometer arrangement is embodied in a solid state waveguide configuration called the multiple path length dual polarization interferometer (MPL-DPI). The technique is demonstrated with ultrathin layers of poly(methylmethacrylate) and human serum albumin.

It is widely assumed that the dominant source of scattering in graphene is charged impurities in a substrate. We have tested this conjecture by studying graphene placed on various substrates and in high-kappa media. Unexpectedly, we have found no significant changes in carrier mobility either for different substrates or by using glycerol, ethanol, and water as a top dielectric layer. This suggests that Coulomb impurities are not the scattering mechanism that limits the mean free path attainable for graphene on a substrate.

We experimentally demonstrate extremely narrow plasmon resonances with half-width of just several nanometers in regular arrays of metallic nanoparticles. These resonances are observed at Rayleigh's cutoff wavelengths for Wood anomalies and based on diffraction coupling of localized plasmons. We show experimentally that reflection from an array of nanoparticles can be completely suppressed at certain wavelengths. As a result, our metal nanostructures exhibit pi-jump for the phase of the reflected light.

Graphene is only one atom thick, optically transparent, chemically inert, and an excellent conductor. These properties seem to make this material an excellent candidate for applications in various photonic devices that require conducting but transparent thin films. In this letter, we demonstrate liquid crystal devices with electrodes made of graphene that show excellent performance with a high contrast ratio. We also discuss the advantages of graphene compared to conventionally used metal oxides in terms of low resistivity, high transparency and chemical stability.

We have studied temperature dependences of electron transport in graphene and its bilayer and found extremely low electron-phonon scattering rates that set the fundamental limit on possible charge carrier mobilities at room temperature. Our measurements show that mobilities higher than 200 000 cm2/V s are achievable, if extrinsic disorder is eliminated. A sharp (thresholdlike) increase in resistivity observed above approximately 200 K is unexpected but can qualitatively be understood within a model of a rippled graphene sheet in which scattering occurs on intraripple flexural phonons.

Low-field magnetoresistance is ubiquitous in low-dimensional metallic systems with high resistivity and well understood as arising due to quantum interference on self-intersecting diffusive trajectories. We have found that in graphene this weak-localization magnetoresistance is strongly suppressed and, in some cases, completely absent. The unexpected observation is attributed to mesoscopic corrugations of graphene sheets which can cause a dephasing effect similar to that of a random magnetic field.

The structures of the polar surfaces of ZnO are studied using ab initio calculations and surface x-ray diffraction. The experimental and theoretical relaxations are in good agreement. The polar surfaces are shown to be very stable; the cleavage energy for the (0001)-Zn and (0001;)-O surfaces is 4.0 J/m(2) comparable to 2.32 J/m(2) for the most stable nonpolar (1010) surface. The surfaces are stabilized by an electronic mechanism involving the transfer of 0.17 electrons between them. This leads to 2D metallic surface states, which has implications for the use of the material in gas sensing and catalytic applications.