Graphene-based materials can have well-defined nanometer pores and can exhibit low frictional water flow inside them, making their properties of interest for filtration and separation. We investigate ...permeation through micrometer-thick laminates prepared by means of vacuum filtration of graphene oxide suspensions. The laminates are vacuum-tight in the dry state but, if immersed in water, act as molecular sieves, blocking all solutes with hydrated radii larger than 4.5 angstroms. Smaller ions permeate through the membranes at rates thousands of times faster than what is expected for simple diffusion. We believe that this behavior is caused by a network of nanocapillaries that open up in the hydrated state and accept only species that fit in. The anomalously fast permeation is attributed to a capillary-like high pressure acting on ions inside graphene capillaries.
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.
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.
Flexible barrier films preventing permeation of gases and moistures are important for many industries ranging from food to medical and from chemical to electronic. From this perspective, graphene has ...recently attracted particular interest because its defect-free monolayers are impermeable to all atoms and molecules. However, it has been proved to be challenging to develop large-area defectless graphene films suitable for industrial use. Here we report barrier properties of multilayer graphitic films made by gentle chemical reduction of graphene oxide laminates with hydroiodic and ascorbic acids. They are found to be highly impermeable to all gases, liquids and aggressive chemicals including, for example, hydrofluoric acid. The exceptional barrier properties are attributed to a high degree of graphitization of the laminates and little structural damage during reduction. This work indicates a close prospect of graphene-based flexible and inert barriers and protective coatings, which can be of interest for numerous applications.
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.
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.
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.
We report properties of a plasmonic nanoarray coupled to a single layered graphene sheet transferred on the top of the nanoarray. We observe significant (up to 1000 times) enhancements of resonant ...Raman scattering from a graphene layer generated by near fields of a plasmonic nanoarray. This enhancement is quantitatively explained by the electromagnetic mechanism. We experimentally demonstrate a significant spectral shift of diffractive coupled plasmon resonances induced by the graphene presence and show that the collective plasmon resonances can be used to study surface chemistry of graphene. Our results emphasize prospective capabilities of graphene-functionalized plasmonics.
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