Electrically controlled water permeation through graphene oxide membranes.

Controlled transport of water molecules through membranes and capillaries is important in areas as diverse as water purification and healthcare technologies1-7. Previous attempts to control water permeation through membranes (mainly polymeric ones) have concentrated on modulating the structure of the membrane and the physicochemical properties of its surface by varying the pH, temperature or ionic strength3,8. Electrical control over water transport is an attractive alternative; however, theory and simulations9-14 have often yielded conflicting results, from freezing of water molecules to melting of ice14-16 under an applied electric field. Here we report electrically controlled water permeation through micrometre-thick graphene oxide membranes17-21. Such membranes have previously been shown to exhibit ultrafast permeation of water17,22 and molecular sieving properties18,21, with the potential for industrial-scale production. To achieve electrical control over water permeation, we create conductive filaments in the graphene oxide membranes via controllable electrical breakdown. The electric field that concentrates around these current-carrying filaments ionizes water molecules inside graphene capillaries within the graphene oxide membranes, which impedes water transport. We thus demonstrate precise control of water permeation, from ultrafast permeation to complete blocking. Our work opens up an avenue for developing smart membrane technologies for artificial biological systems, tissue engineering and filtration.

Plasmonic Surface Lattice Resonances: A Review of Properties and Applications.

When metal nanoparticles are arranged in an ordered array, they may scatter light to produce diffracted waves. If one of the diffracted waves then propagates in the plane of the array, it may couple the localized plasmon resonances associated with individual nanoparticles together, leading to an exciting phenomenon, the drastic narrowing of plasmon resonances, down to 1-2 nm in spectral width. This presents a dramatic improvement compared to a typical single particle resonance line width of >80 nm. The very high quality factors of these diffractively coupled plasmon resonances, often referred to as plasmonic surface lattice resonances, and related effects have made this topic a very active and exciting field for fundamental research, and increasingly, these resonances have been investigated for their potential in the development of practical devices for communications, optoelectronics, photovoltaics, data storage, biosensing, and other applications. In the present review article, we describe the basic physical principles and properties of plasmonic surface lattice resonances: the width and quality of the resonances, singularities of the light phase, electric field enhancement, etc. We pay special attention to the conditions of their excitation in different experimental architectures by considering the following: in-plane and out-of-plane polarizations of the incident light, symmetric and asymmetric optical (refractive index) environments, the presence of substrate conductivity, and the presence of an active or magnetic medium. Finally, we review recent progress in applications of plasmonic surface lattice resonances in various fields.

Ultrathin graphene-based membrane with precise molecular sieving and ultrafast solvent permeation.

Graphene oxide (GO) membranes continue to attract intense interest due to their unique molecular sieving properties combined with fast permeation. However, their use is limited to aqueous solutions because GO membranes appear impermeable to organic solvents, a phenomenon not yet fully understood. Here, we report efficient and fast filtration of organic solutions through GO laminates containing smooth two-dimensional (2D) capillaries made from large (10-20 µm) flakes. Without modification of sieving characteristics, these membranes can be made exceptionally thin, down to ∼10 nm, which translates into fast water and organic solvent permeation. We attribute organic solvent permeation and sieving properties to randomly distributed pinholes interconnected by short graphene channels with a width of 1 nm. With increasing membrane thickness, organic solvent permeation rates decay exponentially but water continues to permeate quickly, in agreement with previous reports. The potential of ultrathin GO laminates for organic solvent nanofiltration is demonstrated by showing >99.9% rejection of small molecular weight organic dyes dissolved in methanol. Our work significantly expands possibilities for the use of GO membranes in purification and filtration technologies.

Graphene light modulators working at near-infrared wavelengths.

We demonstrate a graphene-based electro-absorption modulator with extremely small modulation volume that can be controlled by low gating voltages 1-3 V and shows light modulation at wavelengths as short as 900 nm. Our choice of hafnium oxide dielectric separator gives the possibility to obtain significant electro-optical effect in a simple optical heterostructure. Having low power consumption, our devices could find a wide range of applications in telecom industry.

New class of photocatalytic materials and a novel principle for efficient water splitting under infrared and visible light: MgB2 as unexpected example.

Water splitting is unanimously recognized as environment friendly, potentially low cost and renewable energy solution based on the future hydrogen economy. Especially appealing is photocatalytic water splitting whereby a suitably chosen catalyst dramatically improves efficiency of the hydrogen production driven by direct sunlight and allows it to happen even at zero driving potential. Here, we suggest a new class of stable photocatalysts and the corresponding principle for catalytic water splitting in which infrared and visible light play the main role in producing the photocurrent and hydrogen. The new class of catalysts - ionic or covalent binary metals with layered graphite-like structures - effectively absorb visible and infrared light facilitating the reaction of water splitting, suppress the inverse reaction of ion recombination by separating ions due to internal electric fields existing near alternating layers, provide the sites for ion trapping of both polarities, and finally deliver the electrons and holes required to generate hydrogen and oxygen gases. As an example, we demonstrate conversion efficiency of ~27% at bias voltage Vbias = 0.5V for magnesium diboride working as a catalyst for photoinduced water splitting. We discuss its advantages over some existing materials and propose the underlying mechanism of photocatalytic water splitting by binary layered metals.

Engineering optical properties of a graphene oxide metamaterial assembled in microfluidic channels.

The dense packing of two dimensional flakes by van der Waals forces has enabled the creation of new metamaterials with desirable optical properties. Here we assemble graphene oxide sheets into a three dimensional metamaterial using a microfluidic technique and confirm their ordering via measurements of ellipsometric parameters, polarized optical microscopy, polarized transmission spectroscopy, infrared spectroscopy and scanning electron microscopy. We show that the produced metamaterials demonstrate strong in-plane optical anisotropy (Δn≈0.3 at n≈1.5-1.8) combined with low absorption (k<0.1) and compare them with as-synthesized samples of graphene oxide paper. Our results pave the way for engineered birefringent metamaterials on the basis of two dimensional atomic crystals including graphene and its derivatives.

Singular phase nano-optics in plasmonic metamaterials for label-free single-molecule detection.

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.

Nanofabricated media with negative permeability at visible frequencies.

A great deal of attention has recently been focused on a new class of smart materials--so-called left-handed media--that exhibit highly unusual electromagnetic properties and promise new device applications. Left-handed materials require negative permeability micro, an extreme condition that has so far been achieved only for frequencies in the microwave to terahertz range. Extension of the approach described in ref. 7 to achieve the necessary high-frequency magnetic response in visible optics presents a formidable challenge, as no material--natural or artificial--is known to exhibit any magnetism at these frequencies. Here we report a nanofabricated medium consisting of electromagnetically coupled pairs of gold dots with geometry carefully designed at a 10-nm level. The medium exhibits a strong magnetic response at visible-light frequencies, including a band with negative micro. The magnetism arises owing to the excitation of an antisymmetric plasmon resonance. The high-frequency permeability qualitatively reveals itself via optical impedance matching. Our results demonstrate the feasibility of engineering magnetism at visible frequencies and pave the way towards magnetic and left-handed components for visible optics.

Composite au nanostructures for fluorescence studies in visible light.

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.

Giant optical anisotropy in transition metal dichalcogenides for next-generation photonics.

Large optical anisotropy observed in a broad spectral range is of paramount importance for efficient light manipulation in countless devices. Although a giant anisotropy has been recently observed in the mid-infrared wavelength range, for visible and near-infrared spectral intervals, the problem remains acute with the highest reported birefringence values of 0.8 in BaTiS3 and h-BN crystals. This issue inspired an intensive search for giant optical anisotropy among natural and artificial materials. Here, we demonstrate that layered transition metal dichalcogenides (TMDCs) provide an answer to this quest owing to their fundamental differences between intralayer strong covalent bonding and weak interlayer van der Waals interaction. To do this, we made correlative far- and near-field characterizations validated by first-principle calculations that reveal a huge birefringence of 1.5 in the infrared and 3 in the visible light for MoS2. Our findings demonstrate that this remarkable anisotropy allows for tackling the diffraction limit enabling an avenue for on-chip next-generation photonics.

Sensitivity of collective plasmon modes of gold nanoresonators to local environment.

We present what we believe to be the first experimental study of the optical response of collective plasmon resonances in regular arrays of nanoresonators to local environment. Recently observed collective plasmon modes arise due to diffractive coupling of localized plasmons and yield almost 1 order of magnitude improvement in resonance quality. We measure the response of these modes to tiny variations of the refractive index of both gaseous and liquid media. We show that the phase sensitivity of the collective resonances can be more than 2 orders of magnitude better than the best amplitude sensitivity of the same nanodot array as well as 1 order of magnitude better than the phase sensitivity in surface plasmon resonance sensors.

Cascaded optical field enhancement in composite plasmonic nanostructures.

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.

Layered material platform for surface plasmon resonance biosensing.

Plasmonic biosensing has emerged as the most sensitive label-free technique to detect various molecular species in solutions and has already proved crucial in drug discovery, food safety and studies of bio-reactions. This technique relies on surface plasmon resonances in ~50 nm metallic films and the possibility to functionalize the surface of the metal in order to achieve selectivity. At the same time, most metals corrode in bio-solutions, which reduces the quality factor and darkness of plasmonic resonances and thus the sensitivity. Furthermore, functionalization itself might have a detrimental effect on the quality of the surface, also reducing sensitivity. Here we demonstrate that the use of graphene and other layered materials for passivation and functionalization broadens the range of metals which can be used for plasmonic biosensing and increases the sensitivity by 3-4 orders of magnitude, as it guarantees stability of a metal in liquid and preserves the plasmonic resonances under biofunctionalization. We use this approach to detect low molecular weight HT-2 toxins (crucial for food safety), achieving phase sensitivity~0.5 fg/mL, three orders of magnitude higher than previously reported. This proves that layered materials provide a new platform for surface plasmon resonance biosensing, paving the way for compact biosensors for point of care testing.

Applied optics. Gain modulation by graphene plasmons in aperiodic lattice lasers.

Two-dimensional graphene plasmon-based technologies will enable the development of fast, compact, and inexpensive active photonic elements because, unlike plasmons in other materials, graphene plasmons can be tuned via the doping level. Such tuning is harnessed within terahertz quantum cascade lasers to reversibly alter their emission. This is achieved in two key steps: first, by exciting graphene plasmons within an aperiodic lattice laser and, second, by engineering photon lifetimes, linking graphene's Fermi energy with the round-trip gain. Modal gain and hence laser spectra are highly sensitive to the doping of an integrated, electrically controllable, graphene layer. Demonstration of the integrated graphene plasmon laser principle lays the foundation for a new generation of active, programmable plasmonic metamaterials with major implications across photonics, material sciences, and nanotechnology.

Superconductivity in Ca-doped graphene laminates.

Despite graphene's long list of exceptional electronic properties and many theoretical predictions regarding the possibility of superconductivity in graphene, its direct and unambiguous experimental observation has not been achieved. We searched for superconductivity in weakly interacting, metal decorated graphene crystals assembled into so-called graphene laminates, consisting of well separated and electronically decoupled graphene crystallites. We report robust superconductivity in all Ca-doped graphene laminates. They become superconducting at temperatures (Tc) between ≈4 and ≈6 K, with Tc's strongly dependent on the confinement of the Ca layer and the induced charge carrier concentration in graphene. We find that Ca is the only dopant that induces superconductivity in graphene laminates above 1.8 K among several dopants used in our experiments, such as potassium, caesium and lithium. By revealing the tunability of the superconducting response through doping and confinement of the metal layer, our work shows that achieving superconductivity in free-standing, metal decorated monolayer graphene is conditional on an optimum confinement of the metal layer and sufficient doping, thereby bringing its experimental realization within grasp.

Sieving hydrogen isotopes through two-dimensional crystals.

One-atom-thick crystals are impermeable to atoms and molecules, but hydrogen ions (thermal protons) penetrate through them. We show that monolayers of graphene and boron nitride can be used to separate hydrogen ion isotopes. Using electrical measurements and mass spectrometry, we found that deuterons permeate through these crystals much slower than protons, resulting in a separation factor of ≈10 at room temperature. The isotope effect is attributed to a difference of ≈60 milli-electron volts between zero-point energies of incident protons and deuterons, which translates into the equivalent difference in the activation barriers posed by two-dimensional crystals. In addition to providing insight into the proton transport mechanism, the demonstrated approach offers a competitive and scalable way for hydrogen isotope enrichment.

Nanomechanical electro-optical modulator based on atomic heterostructures.

Two-dimensional atomic heterostructures combined with metallic nanostructures allow one to realize strong light-matter interactions. Metallic nanostructures possess plasmonic resonances that can be modulated by graphene gating. In particular, spectrally narrow plasmon resonances potentially allow for very high graphene-enabled modulation depth. However, the modulation depths achieved with this approach have so far been low and the modulation wavelength range limited. Here we demonstrate a device in which a graphene/hexagonal boron nitride heterostructure is suspended over a gold nanostripe array. A gate voltage across these devices alters the location of the two-dimensional crystals, creating strong optical modulation of its reflection spectra at multiple wavelengths: in ultraviolet Fabry-Perot resonances, in visible and near-infrared diffraction-coupled plasmonic resonances and in the mid-infrared range of hexagonal boron nitride's upper Reststrahlen band. Devices can be extremely subwavelength in thickness and exhibit compact and truly broadband modulation of optical signals using heterostructures of two-dimensional materials.

Hybrid graphene plasmonic waveguide modulators.

The unique optical and electronic properties of graphene make possible the fabrication of novel optoelectronic devices. One of the most exciting graphene characteristics is the tunability by gating which allows one to realize active optical devices. While several types of graphene-based photonic modulators have already been demonstrated, the potential of combining the versatility of graphene with subwavelength field confinement of plasmonic waveguides remains largely unexplored. Here we report fabrication and study of hybrid graphene-plasmonic waveguide modulators. We consider several types of modulators and identify the most promising one for telecom applications. The modulator working at the telecom range is demonstrated, showing a modulation depth of >0.03 dB µm(-1) at low gating voltages for an active device area of just 10 µm(2), characteristics which are already comparable to those of silicon-based waveguide modulators while retaining the benefit of further device miniaturization. Our proof-of-concept results pave the way towards on-chip realization of efficient graphene-based active plasmonic waveguide devices for optical communications.

Graphene-protected copper and silver plasmonics.

Plasmonics has established itself as a branch of physics which promises to revolutionize data processing, improve photovoltaics, and increase sensitivity of bio-detection. A widespread use of plasmonic devices is notably hindered by high losses and the absence of stable and inexpensive metal films suitable for plasmonic applications. To this end, there has been a continuous search for alternative plasmonic materials that are also compatible with complementary metal oxide semiconductor technology. Here we show that copper and silver protected by graphene are viable candidates. Copper films covered with one to a few graphene layers show excellent plasmonic characteristics. They can be used to fabricate plasmonic devices and survive for at least a year, even in wet and corroding conditions. As a proof of concept, we use the graphene-protected copper to demonstrate dielectric loaded plasmonic waveguides and test sensitivity of surface plasmon resonances. Our results are likely to initiate wide use of graphene-protected plasmonics.

Strong light-matter interactions in heterostructures of atomically thin films.

The isolation of various two-dimensional (2D) materials, and the possibility to combine them in vertical stacks, has created a new paradigm in materials science: heterostructures based on 2D crystals. Such a concept has already proven fruitful for a number of electronic applications in the area of ultrathin and flexible devices. Here, we expand the range of such structures to photoactive ones by using semiconducting transition metal dichalcogenides (TMDCs)/graphene stacks. Van Hove singularities in the electronic density of states of TMDC guarantees enhanced light-matter interactions, leading to enhanced photon absorption and electron-hole creation (which are collected in transparent graphene electrodes). This allows development of extremely efficient flexible photovoltaic devices with photoresponsivity above 0.1 ampere per watt (corresponding to an external quantum efficiency of above 30%).