Mid-infrared plasmonic biosensing with graphene Rodrigo, Daniel; Limaj, Odeta; Janner, Davide ...
Science (American Association for the Advancement of Science),
07/2015, Letnik:
349, Številka:
6244
Journal Article
Recenzirano
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Infrared spectroscopy is the technique of choice for chemical identification of biomolecules through their vibrational fingerprints. However, infrared light interacts poorly with nanometric-size ...molecules. We exploit the unique electro-optical properties of graphene to demonstrate a high-sensitivity tunable plasmonic biosensor for chemically specific label-free detection of protein monolayers. The plasmon resonance of nanostructured graphene is dynamically tuned to selectively probe the protein at different frequencies and extract its complex refractive index. Additionally, the extreme spatial light confinement in graphene–up to two orders of magnitude higher than in metals–produces an unprecedentedly high overlap with nanometric biomolecules, enabling superior sensitivity in the detection of their refractive index and vibrational fingerprints. The combination of tunable spectral selectivity and enhanced sensitivity of graphene opens exciting prospects for biosensing.
We advocate the widespread use of UV-C light as a short-term, easily deployable, and affordable way to limit virus spread in the current SARS-CoV-2 pandemic. Radical social distancing with the ...associated shutdown of schools, restaurants, sport clubs, workplaces, and traveling has been shown to be effective in reducing virus spread, but its economic and social costs are unsustainable in the medium term. Simple measures like frequent handwashing, facial masks, and other physical barriers are being commonly adopted to prevent virus transmission. However, their efficacy may be limited, particularly in shared indoor spaces, where, in addition to airborne transmission, elements with small surface areas such as elevator buttons, door handles, and handrails are frequently used and can also mediate transmission. We argue that additional measures are necessary to reduce virus transmission when people resume attending schools and jobs that require proximity or some degree of physical contact. Among the available alternatives, UV-C light satisfies the requirements of rapid, widespread, and economically viable deployment. Its implementation is only limited by current production capacities, an increase of which requires swift intervention by industry and authorities.
Progress in electron-beam spectroscopies has recently enabled the study of optical excitations with combined space, energy and time resolution in the nanometre, millielectronvolt and femtosecond ...domain, thus providing unique access into nanophotonic structures and their detailed optical responses. These techniques rely on ~1-300 keV electron beams focused at the sample down to sub-nanometre spots, temporally compressed in wavepackets a few femtoseconds long, and in some cases controlled by ultrafast light pulses. The electrons undergo energy losses and gains (also giving rise to cathodoluminescence light emission), which are recorded to reveal the optical landscape along the beam path. This Review portraits these advances, with a focus on coherent excitations, emphasizing the increasing level of control over the electron wavefunctions and ensuing applications in the study and technological use of optically resonant modes and polaritons in nanoparticles, 2D materials and engineered nanostructures.
The ability to manipulate optical fields and the energy flow of light is central to modern information and communication technologies, as well as quantum information processing schemes. However, ...because photons do not possess charge, a way of controlling them efficiently by electrical means has so far proved elusive. A promising way to achieve electric control of light could be through plasmon polaritons—coupled excitations of photons and charge carriers—in graphene. In this two-dimensional sheet of carbon atoms, it is expected that plasmon polaritons and their associated optical fields can readily be tuned electrically by varying the graphene carrier density. Although evidence of optical graphene plasmon resonances has recently been obtained spectroscopically, no experiments so far have directly resolved propagating plasmons in real space. Here we launch and detect propagating optical plasmons in tapered graphene nanostructures using near-field scattering microscopy with infrared excitation light. We provide real-space images of plasmon fields, and find that the extracted plasmon wavelength is very short—more than 40 times smaller than the wavelength of illumination. We exploit this strong optical field confinement to turn a graphene nanostructure into a tunable resonant plasmonic cavity with extremely small mode volume. The cavity resonance is controlled in situ by gating the graphene, and in particular, complete switching on and off of the plasmon modes is demonstrated, thus paving the way towards graphene-based optical transistors. This successful alliance between nanoelectronics and nano-optics enables the development of active subwavelength-scale optics and a plethora of nano-optoelectronic devices and functionalities, such as tunable metamaterials, nanoscale optical processing, and strongly enhanced light–matter interactions for quantum devices and biosensing applications.
We exploit free-space interactions between electron beams and tailored light fields to imprint on-demand phase profiles on the electron wave functions. Through rigorous semiclassical theory involving ...a quantum description of the electrons, we show that monochromatic optical fields focused in vacuum can be used to correct electron beam aberrations and produce selected focal shapes. Stimulated elastic Compton scattering is exploited to imprint the required electron phase, which is proportional to the integral of the optical field intensity along the electron path and depends on the transverse beam position. The required light intensities are attainable in currently available ultrafast electron microscope setups, thus opening the field of free-space optical manipulation of electron beams.
Graphene plasmons provide a suitable alternative to noble-metal plasmons because they exhibit much tighter confinement and relatively long propagation distances, with the advantage of being highly ...tunable via electrostatic gating. Here, we propose to use graphene plasmons as a platform for strongly enhanced light–matter interactions. Specifically, we predict unprecedented high decay rates of quantum emitters in the proximity of a carbon sheet, observable vacuum Rabi splittings, and extinction cross sections exceeding the geometrical area in graphene nanoribbons and nanodisks. Our theoretical results provide the basis for the emerging and potentially far-reaching field of graphene plasmonics, offering an ideal platform for cavity quantum electrodynamics, and supporting the possibility of single-molecule, single-plasmon devices.
Identification of gas molecules plays a key role a wide range of applications extending from healthcare to security. However, the most widely used gas nano-sensors are based on electrical approaches ...or refractive index sensing, which typically are unable to identify molecular species. Here, we report label-free identification of gas molecules SO
, NO
, N
O, and NO by detecting their rotational-vibrational modes using graphene plasmon. The detected signal corresponds to a gas molecule layer adsorbed on the graphene surface with a concentration of 800 zeptomole per μm
, which is made possible by the strong field confinement of graphene plasmons and high physisorption of gas molecules on the graphene nanoribbons. We further demonstrate a fast response time (<1 min) of our devices, which enables real-time monitoring of gaseous chemical reactions. The demonstration and understanding of gas molecule identification using graphene plasmonic nanostructures open the door to various emerging applications, including in-breath diagnostics and monitoring of volatile organic compounds.
When an Au nanoparticle in a liquid medium is illuminated with resonant light of sufficient intensity, a nanometer scale envelope of vapora “nanobubble”surrounding the particle, is formed. This is ...the nanoscale onset of the well-known process of liquid boiling, occurring at a single nanoparticle nucleation site, resulting from the photothermal response of the nanoparticle. Here we examine bubble formation at an individual metallic nanoparticle in detail. Incipient nanobubble formation is observed by monitoring the plasmon resonance shift of an individual, illuminated Au nanoparticle, when its local environment changes from liquid to vapor. The temperature on the nanoparticle surface is monitored during this process, where a dramatic temperature jump is observed as the nanoscale vapor layer thermally decouples the nanoparticle from the surrounding liquid. By increasing the intensity of the incident light or decreasing the interparticle separation, we observe the formation of micrometer-sized bubbles resulting from the coalescence of nanoparticle-“bound” vapor envelopes. These studies provide the first direct and quantitative analysis of the evolution of light-induced steam generation by nanoparticles from the nanoscale to the macroscale, a process that is of fundamental interest for a growing number of applications.
Molecular chemistry offers a unique toolkit to draw inspiration for the design of artificial metamolecules. For a long time, optical circular dichroism has been exclusively the terrain of natural ...chiral molecules, which exhibit optical activity mainly in the UV spectral range, thus greatly hindering their significance for a broad range of applications. Here we demonstrate that circular dichroism can be generated with artificial plasmonic chiral nanostructures composed of the minimum number of spherical gold nanoparticles required for three-dimensional (3D) chirality. We utilize a rigid addressable DNA origami template to precisely organize four nominally identical gold nanoparticles into a three-dimensional asymmetric tetramer. Because of the chiral structural symmetry and the strong plasmonic resonant coupling between the gold nanoparticles, the 3D plasmonic assemblies undergo different interactions with left and right circularly polarized light, leading to pronounced circular dichroism. Our experimental results agree well with theoretical predictions. The simplicity of our structure geometry and, most importantly, the concept of resorting on biology to produce artificial photonic functionalities open a new pathway to designing smart artificial plasmonic nanostructures for large-scale production of optically active metamaterials.
Plasmonically enhanced optical dichroism has attracted substantial interest for its application in optical sensing, where the interplay between chirality emanating from both molecules and ...plasmon-supporting structures has been regarded as a critical ingredient. Here, we experimentally demonstrate that suitably self-assembled achiral plasmonic nanostructures produce a high degree of enhancement in the optical dichroism observed from chiral molecules placed in their vicinity. Specifically, we identify a near-field enhancement associated with plasmonic hotpots as the mechanism enabling our observation of visible-NIR circular dichroism emanating from small amounts of chiral molecules. Our structures consist of linear arrays of gold nanorods obtained by introducing chiral anionic surfactants, such as modified bile salts, which lead to selective destabilization of a cetyltrimethylammonium bromide coating layer on Au nanorods, thereby promoting a tip-to-tip oriented assembly. The proposed mechanism of plasmonically-enhanced circular dichroism is supported by deriving a simple, yet general theoretical formalism that confirms the observed results, revealing the role of optical hotspots at the gaps of linear tip-to-tip nanorod assemblies as the origin of enhancement in the dichroism from chiral molecules. Importantly, it is the refractive rather than the absorption-mediated chiral response of the molecules that produces dichroism in the visible-NIR plasmonic regime, far from their UV absorption resonances. The observed self-assembly mechanism suggests that chiral analytes not directly interacting with the nanorod surfaces, but just able to induce tip-to-tip aggregation, can be revealed by a CD signature in the plasmonic region, thereby supporting potential applications in ultrasensitive analysis.
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