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We present a first-principles theoretical study of the atomistic footprints in the valence electron energy loss spectroscopy (EELS) of nanometer-size metallic particles. Charge density maps of excited plasmons and EEL spectra for specific electron paths through a nanoparticle (Na380 atom cluster) are modeled using ab initio calculations within time-dependent density functional theory. Our findings unveil the atomic-scale sensitivity of EELS within this low-energy spectral range. Whereas localized surface plasmons (LSPs) are particularly sensitive to the atomistic structure of the surface probed by the electron beam, confined bulk plasmons (CBPs) reveal quantum size effects within the nanoparticle's volume. Moreover, we prove that classical local dielectric theories mimicking the atomistic structure of the nanoparticles reproduce the LSP trends observed in quantum calculations, but fall short in describing the CBP behavior observed under different electron trajectories.
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When an organic molecule is placed inside a plasmonic cavity formed by two metallic nanoparticles (MNP) under illumination, the electronic excitations of the molecule couple to the plasmonic electromagnetic modes of the cavity, inducing new hybrid light-matter states called polaritons. Atomistic ab initio methods accurately describe the coupling between MNPs and molecules at the nanometer scale and allow us to analyze how atomistic features influence the interaction. In this work, we study the optical response of a porphine molecule coupled to a silver nanoparticle dimer from first principles, within the linear-response time-dependent density functional theory framework, using the recently developed Python Numeric Atomic Orbitals implementation to compute the optical excitations. The optical spectra show the splitting of the resonances of the plasmonic dimer and the molecule into two distinct polaritons, a characteristic feature of the strong light-matter coupling regime. Our results stress the importance of atomistic features, such as the gap configuration in determining the plasmon-exciton coupling strength and in the emergence of molecule-mediated charge-transfer plasmon (CTP) resonances at lower frequencies. Moreover, we show that the strength of the CTP resonance can be tuned by shifting the alignment of the molecular energy levels with respect to the Fermi level of the MNPs.
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Complementary metasurfaces composed of randomly-placed arrays of aligned rods or slits are fabricated out of giant magnetoresistance Ni81Fe19/Au multilayers (MLs), a material whose optical properties change under the application of an external static magnetic field. The two metasurfaces are studied from both the experimental and theoretical viewpoints. The induced magnetic modulation (MM) of both the far-field signal and the resonant near field, at the rod/slit localized surface plasmon frequency, are found to obey the Babinet's principle. Furthermore, the near-field MM is found to be higher than the far-field counterpart. At resonance, both arrays show spots with high values of the magnetic modulated intensity of the electric near field (MM hot-spots). We show that this high magnetic modulation of the near-field intensity is very promising for the future development of high sensitivity molecular sensing platforms in the Mid- and Far-IR, using Magnetic-Modulation of Surface-Enhanced Infrared Absorption (MM-SEIRA) spectroscopy.
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We present a novel concept of a magnetically tunable plasmonic crystal based on the excitation of Fano lattice surface modes in periodic arrays of magnetic and optically anisotropic nanoantennas. We show how coherent diffractive far-field coupling between elliptical nickel nanoantennas is governed by the two in-plane, orthogonal and spectrally detuned plasmonic responses of the individual building block, one directly induced by the incident radiation and the other induced by the application of an external magnetic field. The consequent excitation of magnetic field-induced Fano lattice surface modes leads to highly tunable and amplified magneto-optical effects as compared to a continuous film or metasurfaces made of disordered noninteracting magnetoplasmonic anisotropic nanoantennas. The concepts presented here can be exploited to design novel magnetoplasmonic sensors based on coupled localized plasmonic resonances, and nanoscale metamaterials for precise control and magnetically driven tunability of light polarization states.
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We present a theoretical study of a metal-molecular aggregate hybrid system consisting of a strongly coupled dimer connected by molecules characterized by an excitonic transition. The plasmonic resonances of the metallic dimer interact with the molecular excitations giving rise to coupled plasmon-exciton states, so called plexcitons. We compare the differences in the optical response when the excitonic material is placed only as a linker in the plasmonic gap of the dimer and when the material is distributed as an aggregate layer covering the dimer entirely. We also explore the efficiency of plexcitons for localized surface plamon resonance (LSPR) sensing in both situations. The ordinary shift-based sensing is more efficient for dimers connected through molecular linkers, whereas intensity-based sensing is more effective when the molecular aggregate covers the entire nanostructure. These results can serve to design the chemistry of excitons around metallic nanoparticles.
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Multivariate analysis applied in biosensing greatly improves analytical performance by extracting relevant information or bypassing confounding factors such as nonlinear responses or experimental errors and noise. Plasmonic sensors based on various light coupling mechanisms have shown impressive performance in biosensing by detecting dielectric changes with high sensitivity. In this study, gold nanodiscs are used as metasurface in a Kretschmann setup, and a variety of features from the reflectance curve are used by machine learning to improve sensing performance. The nanostructures of the metasurface generate new plasmonic features, apart from the typical resonance that occurs in the classical Kretschmann mode of a gold thin film, related to the evanescent field beyond total internal reflection. When the engineered metasurface is integrated into a microfluidic chamber, the device provides additional spectral features generated by Fresnel reflections at all dielectric interfaces. The increased number of features results in greatly improved detection. Here, multivariate analysis enhances analytical sensitivity and sensor resolution by 200% and more than 20%, respectively, and reduces prediction errors by almost 40% compared to a standard plasmonic sensor. The combination of plasmonic metasurfaces and Fresnel reflections thus offers the possibility of improving sensing capabilities even in commonly available setups.
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We present a theoretical study of the optical properties of a strongly coupled metallic dimer when an ensemble of molecules is placed in the inter-particle cavity. The linking molecules are characterized by an excitonic transition which couples to the Bonding Dimer Plasmon (BDP) and the Bonding Quadrupolar Plasmon (BQP) resonances, arising from the hybridization of the dipolar and quadrupolar modes of the individual nanoparticles, respectively. As a consequence, both modes split into two coupled plasmon-exciton modes, so called plexcitons. The Charge Transfer Plasmon (CTP) resonance, involving plasmonic oscillations of the dimer as a whole, arises when the conductance of the excitonic junction is above a threshold value. The possibility of exploiting plexcitonic resonances for sensing is explored in detail. We find high sensitivity to the environment when different dielectric embedding media are considered. Contrary to standard methods, we propose a new framework for effective sensing based on the relative intensity of plexcitonic peaks.
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Spurred by outstanding optical properties, chemical stability, and facile bioconjugation, plasmonic metals have become the first-choice materials for optical signal transducers in biosensing. While the design rules for surface-based plasmonic sensors are well-established and commercialized, there is limited knowledge of the design of sensors based on nanoparticle aggregation. The reason is the lack of control over the interparticle distances, number of nanoparticles per cluster, or multiple mutual orientations during aggregation events, blurring the threshold between positive and negative readout. Here we identify the geometrical parameters (size, shape, and interparticle distance) that allow for maximizing the color difference upon nanoparticle clustering. Finding the optimal structural parameters will provide a fast and reliable means of readout, including unaided eye inspection or computer vision.
Asunto(s)
Oro , Nanopartículas del Metal , Oro/química , Nanopartículas del Metal/química , ColorimetríaRESUMEN
The dynamic restructuring of metal nanoparticle surfaces is known to greatly influence their catalytic, electronic transport, and chemical binding functionalities. Here we show for the first time that non-equilibrium atomic-scale lattice defects can be detected in nanoparticles by purely optical means. These fluctuating states determine interface electronic transport for molecular electronics but because such rearrangements are low energy, measuring their rapid dynamics on single nanostructures by X-rays, electron beams, or tunnelling microscopies, is invasive and damaging. We utilise nano-optics at the sub-5nm scale to reveal rapid (on the millisecond timescale) evolution of defect morphologies on facets of gold nanoparticles on a mirror. Besides dynamic structural information, this highlights fundamental questions about defining bulk plasma frequencies for metals probed at the nanoscale.
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Plasmonic gaps are known to produce nanoscale localization and enhancement of optical fields, providing small effective mode volumes of about a few hundred nm3. Atomistic quantum calculations based on time-dependent density functional theory reveal the effect of subnanometric localization of electromagnetic fields due to the presence of atomic-scale features at the interfaces of plasmonic gaps. Using a classical model, we explain this as a nonresonant lightning rod effect at the atomic scale that produces an extra enhancement over that of the plasmonic background. The near-field distribution of atomic-scale hot spots around atomic features is robust against dynamical screening and spill-out effects and follows the potential landscape determined by the electron density around the atomic sites. A detailed comparison of the field distribution around atomic hot spots from full quantum atomistic calculations and from the local classical approach considering the geometrical profile of the atoms' electronic density validates the use of a classical framework to determine the effective mode volume in these extreme subnanometric optical cavities. This finding is of practical importance for the community of surface-enhanced molecular spectroscopy and quantum nanophotonics, as it provides an adequate description of the local electromagnetic fields around atomic-scale features with use of simplified classical methods.
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The non-physical effects on the transverse momentum transfer from fast electrons to gold nanoparticles associated to the use of non-causal dielectric functions are studied. A direct test of the causality based on the surface Kramers-Kronig relations is presented. This test is applied to the different dielectric function used to describe gold nanostructures in electron microscopy.
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Nanoscale devices in which the interaction with light can be configured using external control signals hold great interest for next-generation optoelectronic circuits. Materials exhibiting a structural or electronic phase transition offer a large modulation contrast with multi-level optical switching and memory functionalities. In addition, plasmonic nanoantennas can provide an efficient enhancement mechanism for both the optically induced excitation and the readout of materials strategically positioned in their local environment. Here, we demonstrate picosecond all-optical switching of the local phase transition in plasmonic antenna-vanadium dioxide (VO2) hybrids, exploiting strong resonant field enhancement and selective optical pumping in plasmonic hotspots. Polarization- and wavelength-dependent pump-probe spectroscopy of multifrequency crossed antenna arrays shows that nanoscale optical switching in plasmonic hotspots does not affect neighboring antennas placed within 100 nm of the excited antennas. The antenna-assisted pumping mechanism is confirmed by numerical model calculations of the resonant, antenna-mediated local heating on a picosecond time scale. The hybrid, nanoscale excitation mechanism results in 20 times reduced switching energies and 5 times faster recovery times than a VO2 film without antennas, enabling fully reversible switching at over two million cycles per second and at local switching energies in the picojoule range. The hybrid solution of antennas and VO2 provides a conceptual framework to merge the field localization and phase-transition response, enabling precise, nanoscale optical memory functionalities.