Material- and shape-dependent optical modes of hyperbolic spheroidal nano-resonators.

Hyperbolic nanoresonators, composed of anisotropic materials with opposite signs of permittivity, have unique optical properties due to a large degree of freedom that hyperbolic dispersion provides in designing their response. Here, we focus on uniaxial hyperbolic nanoresonators composed of a model silver-silica multilayer in the form of spheroids with a broad aspect ratio encompassing both prolate and oblate particles. The origin and evolution of the optical response and mode coupling are investigated using both numerical (T-matrix and FDTD) and theoretical methods. We show the tunability of the optical resonances and the interplay of the shape and material anisotropy in determining the spectral response. Depending on the illumination conditions as well as shape and material anisotropy, a single hyperbolic spheroid can show a dominant electric resonance, behaving as a pure metallic nanoparticle, or a strong dipolar magnetic resonance even in the quasistatic regime. The quasistatic magnetic response of indicates a material-dependent origin of the mode, which is obtained due to coupling of the magnetic and electric multipoles. Such coupling characteristics can be employed in various modern applications based on metasurfaces.

Effect of Benzothiadiazole-Based π-Spacers on Fine-Tuning of Optoelectronic Properties of Oligothiophene-Core Donor Materials for Efficient Organic Solar Cells: A DFT Study.

In this work, five novel A-π-D-π-A type molecules D1-D5 were designed by adding unusual benzothiadiazole derivatives as π-spacer blocks to the efficient reference molecule DRCN5T for application as donor materials in organic solar cells (OSCs). Based on a density functional theory approach, a comprehensive theoretical study was performed with different functionals (B3LYP, B3LYP-GD3, B3LYP-GD3BJ, CAM-B3LYP, M06, M062X, and wB97XD) and with different solvent types (PCM and SMD) at the extended basis set 6-311+g(d,p) to evaluate the structural, optoelectronic, and intramolecular charge transfer properties of these molecules. The B3LYP-GD3BJ hybrid functional was used to optimize the studied molecules in CHCl3 solution with the SMD model solvent as it provided the best results compared to experimental data. Transition density matrix maps were simulated to examine the hole-electron localization and the electronic excitation processes in the excited state, and photovoltaic parameters including open-circuit photovoltage and fill factor were investigated to predict the efficiency of these materials. All the designed materials showed promising optoelectronic and photovoltaic characteristics, and for most of them, a red shift. Out of the proposed molecules, [1,2,5]thiadiazolo[3,4-d]pyridazine was selected as a promising π-spacer block to evaluate its interaction with PC61BM in a composite to understand the charge transfer between the donor and acceptor subparts. Overall, this study showed that adding π-spacer building blocks to the molecular structure is undoubtedly a potential strategy to further enhance the performance of donor materials for OSC applications.

Abundance of cavity-free polaritonic states in resonant materials and nanostructures.

Strong coupling between various kinds of material excitations and optical modes has recently shown potential to modify chemical reaction rates in both excited and ground states. The ground-state modification in chemical reaction rates has usually been reported by coupling a vibrational mode of an organic molecule to the vacuum field of an external optical cavity, such as a planar Fabry-Pérot microcavity made of two metallic mirrors. However, using an external cavity to form polaritonic states might (i) limit the scope of possible applications of such systems and (ii) might be unnecessary. Here, we highlight the possibility of using optical modes sustained by materials themselves to self-couple to their own electronic or vibrational resonances. By tracing the roots of the corresponding dispersion relations in the complex frequency plane, we show that electronic and vibrational polaritons are natural eigenstates of bulk and nanostructured resonant materials that require no external cavity. Several concrete examples such as a slab of the excitonic material and a spherical water droplet in vacuum are shown to reach the regime of such cavity-free self-strong coupling. The abundance of cavity-free polaritons in simple and natural structures points at their relevance and potential practical importance for the emerging field of polaritonic chemistry, exciton transport, and modified material properties.

Dipolar coupling of nanoparticle-molecule assemblies: An efficient approach for studying strong coupling.

Strong light-matter interactions facilitate not only emerging applications in quantum and non-linear optics but also modifications of properties of materials. In particular, the latter possibility has spurred the development of advanced theoretical techniques that can accurately capture both quantum optical and quantum chemical degrees of freedom. These methods are, however, computationally very demanding, which limits their application range. Here, we demonstrate that the optical spectra of nanoparticle-molecule assemblies, including strong coupling effects, can be predicted with good accuracy using a subsystem approach, in which the response functions of different units are coupled only at the dipolar level. We demonstrate this approach by comparison with previous time-dependent density functional theory calculations for fully coupled systems of Al nanoparticles and benzene molecules. While the present study only considers few-particle systems, the approach can be readily extended to much larger systems and to include explicit optical-cavity modes.

Metal-polymer hybrid nanomaterials for plasmonic ultrafast hydrogen detection.

Hydrogen-air mixtures are highly flammable. Hydrogen sensors are therefore of paramount importance for timely leak detection during handling. However, existing solutions do not meet the stringent performance targets set by stakeholders, while deactivation due to poisoning, for example by carbon monoxide, is a widely unsolved problem. Here we present a plasmonic metal-polymer hybrid nanomaterial concept, where the polymer coating reduces the apparent activation energy for hydrogen transport into and out of the plasmonic nanoparticles, while deactivation resistance is provided via a tailored tandem polymer membrane. In concert with an optimized volume-to-surface ratio of the signal transducer uniquely offered by nanoparticles, this enables subsecond sensor response times. Simultaneously, hydrogen sorption hysteresis is suppressed, sensor limit of detection is enhanced, and sensor operation in demanding chemical environments is enabled, without signs of long-term deactivation. In a wider perspective, our work suggests strategies for next-generation optical gas sensors with functionalities optimized by hybrid material engineering.

Effective dipolar polarizability of amorphous arrays of size-dispersed nanoparticles.

Inhomogeneity of nanoparticle size, shape, and distribution is ubiquitous and inherent in fabricated arrays or may be a deliberate attempt to engineer the optical response. It leads to a spread of polarizabilities of interacting elements and phases of scattered light, and quantitative understanding of these effects is important. Focusing on random/amorphous arrays of optical antennas, we combine T-matrix calculations and an analytical approach based on an effective dipolar polarizability within a film of dipoles framework to quantify the spectral response as a function of the particle inhomogeneity and stochastic clustering. The interplay of position-dependent stochastic coupling and size distribution of antennas determines the optical properties of such arrays as a function of mean/standard deviation of diameter and minimum separation. The resonance wavelength, amplitude, and scattering-to-absorption ratio exhibit oscillations around their size-averaged values with periods and amplitudes given by average structural factors.

Ultrafast Modulation of Thermoplasmonic Nanobubbles in Water.

Thermo-optically generated bubbles in water provide a powerful means for active matter control in microfluidic environments. These bubbles are often formed via continuous-wave illumination of an absorbing medium resulting in bubble nucleation via vaporization of water and subsequent bubble growth from the inward diffusion of gas molecules. However, to date, such bubbles tend to be several microns in diameter, resulting in slow dissipation. This limits the dynamic rate, spatial precision, and throughput of operation in any application. Here we show that isolated plasmonic structures can be utilized as highly localized heating elements to generate thermoplasmonic nanobubbles that can be modulated at frequencies up to several kilohertz in water, orders of magnitude faster than previously demonstrated for microbubbles. The nanobubbles are envisioned as advantageous localized active manipulation elements for high throughput microfluidic applications.

Collective Strong Light-Matter Coupling in Hierarchical Microcavity-Plasmon-Exciton Systems.

Polaritons are compositional light-matter quasiparticles that arise as a result of strong coupling between the vacuum field of a resonant optical cavity and electronic excitations in quantum emitters. Reaching such a regime is often hard, as it requires materials possessing high oscillator strengths to interact with the relevant optical mode. Two-dimensional transition metal dichalcogenides (TMDCs) have recently emerged as promising candidates for realization of strong coupling regime at room temperature. However, these materials typically provide coupling strengths in the range of 10-40 meV, which may be insufficient for reaching strong coupling with low quality factor resonators. Here, we demonstrate a universal scheme that allows a straightforward realization of strong coupling with 2D materials and beyond. By intermixing plasmonic excitations in nanoparticle arrays with excitons in a WS2 monolayer inside a resonant metallic microcavity, we fabricate a hierarchical system with the collective microcavity-plasmon-exciton Rabi splitting exceeding ∼500 meV at room temperature. Photoluminescence measurements of the coupled systems show dominant emission from the lower polariton branch, indicating the participation of excitons in the coupling process. Strong coupling has been recently suggested to affect numerous optical- and material-related properties including chemical reactivity, exciton transport, and optical nonlinearities. With the universal scheme presented here, strong coupling across a wide spectral range is within easy reach and therefore exploration of these exciting phenomena can be further pursued in a much broader class of materials.

Observation of Tunable Charged Exciton Polaritons in Hybrid Monolayer WS2-Plasmonic Nanoantenna System.

Formation of dressed light-matter states in optical structures, manifested as Rabi splitting of the eigen energies of a coupled system, is one of the key effects in quantum optics. In pursuing this regime with semiconductors, light is usually made to interact with excitons, electrically neutral quasiparticles of semiconductors; meanwhile interactions with charged three-particle states, trions, have received little attention. Here, we report on strong interaction between localized surface plasmons in silver nanoprisms and excitons and trions in monolayer tungsten disulfide (WS2). We show that the plasmon-exciton interactions in this system can be efficiently tuned by controlling the charged versus neutral exciton contribution to the coupling process. In particular, we show that a stable trion state emerges and couples efficiently to the plasmon resonance at low temperature by forming three bright intermixed plasmon-exciton-trion polariton states. Our findings open up a possibility to exploit electrically charged polaritons at the single nanoparticle level.

Strong Light-Matter Coupling between Plasmons in Individual Gold Bi-pyramids and Excitons in Mono- and Multilayer WSe2.

Monolayer transition-metal dichalcogenides (TMDCs) have attracted a lot of research attention recently, motivated by their remarkable optical properties and potential for strong light-matter interactions. Realization of strong plasmon-exciton coupling is especially desirable in this context because it holds promise for the enabling of room-temperature quantum and nonlinear optical applications. These efforts naturally require investigations at a single-nanoantenna level, which, in turn, should possess a compact optical mode interacting with a small amount of excitonic material. However, standard plasmonic nanoantenna designs such as nanoparticle dimers or particle-on-film suffer from misalignment of the local electric field in the gap with the in-plane transition dipole moment of monolayer TMDCs. Here, we circumvent this problem by utilizing gold bi-pyramids (BPs) as very efficient plasmonic nanoantennas. We demonstrate strong coupling between individual BPs and tungsten diselenide (WSe2) monolayers at room temperature. We further study the coupling between multilayers of WSe2 and BPs to elucidate the effect of the number of layers on the coupling strength. Importantly, BPs adopt a reduced-symmetry configuration when deposited on WSe2, such that only one sharp antenna tip efficiently interacts with excitons. Despite the small interaction area, we manage to achieve strong coupling, with Rabi splitting exceeding ∼100 meV. Our results suggest a feasible way toward realizing plasmon-exciton polaritons involving nanoscopic areas of TMDCs, thus pointing toward quantum and nonlinear optics applications at ambient conditions.

Observation of Mode Splitting in Photoluminescence of Individual Plasmonic Nanoparticles Strongly Coupled to Molecular Excitons.

Plasmon-exciton interactions are important for many prominent spectroscopic applications such as surface-enhanced Raman scattering, plasmon-mediated fluorescence, nanoscale lasing, and strong coupling. The case of strong coupling is analogous to quantum optical effects studied in solid state and atomic systems previously. In plasmonics, similar observations have been almost exclusively made in elastic scattering experiments; however, the interpretation of these experiments is often cumbersome. Here, we demonstrate mode splitting not only in scattering, but also in photoluminescence of individual hybrid nanosystems, which manifests a direct proof of strong coupling in plasmon-exciton nanoparticles. We achieved these results due to saturation of the mode volume with molecular J-aggregates, which resulted in splitting up to 400 meV, that is, ∼20% of the resonance energy. We analyzed the correlation between scattering and photoluminescence and found that splitting in photoluminescence is considerably less than that in scattering. Moreover, we found that splitting in both photoluminescence and scattering signals increased upon cooling to cryogenic temperatures. These findings improve our understanding of strong coupling phenomena in plasmonics.

Wavevector-Selective Nonlinear Plasmonic Metasurfaces.

Electromagnetic metasurfaces with strong nonlinear responses and angular selectivity could offer many new avenues for designing ultrathin optics components. We investigated the optical second harmonic generation from plasmonic metasurfaces composed of aligned gold nanopillars with a pronounced out-of-plane tilt using a flexible nonlinear Fourier microscope. The experimental and computational results demonstrate that these samples function as wavevector-selective nonlinear metasurfaces, that is, the coherent second harmonic signal does not only depend on the polarization and wavelength of the excitation beam, but also of its direction of incidence, in spite of the subwavelength thickness of the active layer. Specifically, we observe that the nonlinear response can vary by almost two orders-of-magnitude when the incidence angle is changed from positive to negative values compared to the surface normal. Further, it is demonstrated that these metasurfaces act as a directional nonlinear mirrors, paving the way for new design of directional meta-mirrors in the nonlinear regime.

Plasmonic Nanospectroscopy for Thermal Analysis of Organic Semiconductor Thin Films.

Organic semiconductors are key materials for the next generation thin film electronic devices like field-effect transistors, light-emitting diodes, and solar cells. Accurate thermal analysis is essential for the fundamental understanding of these materials, for device design, stability studies, and quality control because the desired nanostructures are often far from thermodynamic equilibrium and therefore tend to evolve with time and temperature. However, classical experimental techniques are insufficient because the active layer of most organoelectronic device architectures is typically only on the order of a hundred nanometers or less. Scrutinizing the thermal properties in this size range is, however, critical because strong deviations of the thermal properties from bulk values due to confinement effects and pronounced influence of the substrate become significant. Here, we introduce plasmonic nanospectroscopy as an experimental approach to scrutinize the thickness dependence of the thermal stability of semicrystalline, liquid-crystalline, and glassy organic semiconductor thin films down to the sub-100 nm film thickness regime. In summary, we find a pronounced thickness dependence of the glass transition temperature of ternary polymer/fullerene blend thin films and their constituents, which can be resolved with exceptional precision by the plasmonic nanospectroscopy method, which relies on remarkably simple instrumentation.

Single Particle Nanoplasmonic Sensing in Individual Nanofluidic Channels.

Nanoplasmonics allows label-free optical sensing and spectroscopy at the single nanoparticle level by exploiting plasmonic excitations in metal nanoparticles. Nanofluidics offers exclusive possibilities for applying and controlling fluid flow and mass transport at the nanoscale and toward nanosized objects. Here, we combine these two concepts in a single device, by integrating single particle nanoplasmonic sensing with nanofluidics using advanced nanofabrication. The developed devices enable on-chip referenced parallel single particle nanoplasmonic sensing inside multiple individual nanofluidic channels with dimensions down to the 100 nm range. Beyond detailed discussion of the nanofabrication, general device characterization, and parallelized single particle plasmonic readout concepts, we demonstrate device function on two examples: (i) in situ measurements of local buffer concentrations inside a nanofluidic channel; (ii) real time binding kinetics of alkanethiol molecules to a single plasmonic nanonatenna sensor in a single nanochannel. Our concept thus provides a powerful solution for controlling mass transport to and from individual (plasmonic) nanoparticles, which in a long-term perspective offers unique opportunities for label-free detection of analyte molecules at low concentrations and for fundamental studies of fluids in extreme confinement.

Hydride formation thermodynamics and hysteresis in individual Pd nanocrystals with different size and shape.

Physicochemical properties of nanoparticles may depend on their size and shape and are traditionally assessed in ensemble-level experiments, which accordingly may be plagued by averaging effects. These effects can be eliminated in single-nanoparticle experiments. Using plasmonic nanospectroscopy, we present a comprehensive study of hydride formation thermodynamics in individual Pd nanocrystals of different size and shape, and find corresponding enthalpies and entropies to be nearly size- and shape-independent. The hysteresis observed is significantly wider than in bulk, with details depending on the specifics of individual nanoparticles. Generally, the absorption branch of the hysteresis loop is size-dependent in the sub-30 nm regime, whereas desorption is size- and shape-independent. The former is consistent with a coherent phase transition during hydride formation, influenced kinetically by the specifics of nucleation, whereas the latter implies that hydride decomposition either occurs incoherently or via different kinetic pathways.

Role of material loss and mode volume of plasmonic nanocavities for strong plasmon-exciton interactions.

We investigate the role of material loss and mode volume of plasmonic nanostructures on strong plasmon-exciton coupling. We find that the field enhancement, and therefore loss, is not important for the magnitude of the Rabi splitting as such, but instead it is determined by the mode volume. Nevertheless, for reaching true strong coupling condition, that is, coupling greater than any dissipation, it is important to compromise losses. We also show that using such popular geometries as a dimer of two spheres or bow-tie nanoantennas, does not allow compressing the mode volume much in comparison to a single nanoparticle case, except for very narrow gaps, but rather it allows for efficient extraction of the mode out of the metal thus making it more accessible for excitons to interact with. Even more efficient mode extraction is achieved when high refractive index dielectric is placed in the gap. Our findings may find practical use for quantum plasmonics applications.

Ultimate Limit of Light Extinction by Nanophotonic Structures.

Nanophotonic structures make it possible to precisely engineer the optical response at deep subwavelength scales. However, a fundamental understanding of the general performance limits remains a challenge. Here we use extensive electrodynamics simulations to demonstrate that the so-called f-sum rule sets a strict upper bound to the light extinction by nanostructures regardless their internal interactions and retardation effects. In particular, we show that the f-sum rule applies to arbitrarily complex plasmonic metal structures that exhibit an extraordinary spectral sensitivity to size, shape, near-field coupling effects, and incident polarization. The results may be used for benchmarking light scattering and absorption efficiencies, thus imposing fundamental limits on solar light harvesting, biomedical photonics, and optical communications.

Realizing Strong Light-Matter Interactions between Single-Nanoparticle Plasmons and Molecular Excitons at Ambient Conditions.

Realizing strong light-matter interactions between individual two-level systems and resonating cavities in atomic and solid state systems opens up possibilities to study optical nonlinearities on a single-photon level, which can be useful for future quantum information processing networks. However, these efforts have been hampered by unfavorable experimental conditions, such as cryogenic temperatures and ultrahigh vacuum, required to study such systems and phenomena. Although several attempts to realize strong light-matter interactions at room temperature using plasmon resonances have been made, successful realizations on the single-nanoparticle level are still lacking. Here, we demonstrate the strong coupling between plasmons confined within a single silver nanoprism and excitons in molecular J aggregates at ambient conditions. Our findings show that deep subwavelength mode volumes V together with quality factors Q that are reasonably high for plasmonic nanostructures result in a strong-coupling figure of merit-Q/sqrt[V] as high as ∼6×10^{3} µm^{-3/2}, a value comparable to state-of-the-art photonic crystal and microring resonator cavities. This suggests that plasmonic nanocavities, and specifically silver nanoprisms, can be used for room temperature quantum optics.

Plasmonic glasses: optical properties of amorphous metal-dielectric composites.

Plasmonic glasses composed of metallic inclusions in a host dielectric medium are investigated for their optical properties. Such structures characterized by short-range order can be easily fabricated using bottom-up, self-organization methods and may be utilized in a number of applications, thus, quantification of their properties is important. We show, using T-Matrix calculations of 1D, 2D, and 3D plasmonic glasses, that their plasmon resonance position oscillates as a function of the particle spacing yielding blue- and redshifts up to 0.3 eV in the visible range with respect to the single particle surface plasmon. Their properties are discussed in light of an analytical model of an average particle's polarizability that originates from a coupled dipole methodology.

Surface scattering contribution to the plasmon width in embedded Ag nanospheres.

Nanometer-sized metal particles exhibit broadening of the localized surface plasmon resonance (LSPR) in comparison to its value predicted by the classical Mie theory. Using our model for the LSPR dependence on non-local surface screening and size quantization, we quantitatively relate the observed plasmon width to the nanoparticle radius R and the permittivity of the surrounding medium ε(m). For Ag nanospheres larger than 8 nm only the non-local dynamical effects occurring at the surface are important and, up to a diameter of 25 nm, dominate over the bulk scattering mechanism. Qualitatively, the LSPR width is inversely proportional to the particle size and has a nonmonotonic dependence on the permittivity of the host medium, exhibiting for Ag a maximum at ε(m) ≈ 2.5. Our calculated LSPR width is compared with recent experimental data.