Correlation between Plasmonic and Thermal Properties of Metallic Nanoparticles.

Here, we investigate the correlation between the heat generated by gold nanoparticles, in particular nanospheres and nanobipyramids, and their plasmonic response manifested by the presence of Localized Surface Plasmon Resonances (LSPRs). Using a tunable laser and a thermal camera, we measure the temperature increase induced by colloidal nanoparticles in an aqueous solution as a function of the excitation wavelength in the optical regime. We demonstrate that the photothermal performances of the nanoparticles are strongly related not only to their plasmonic properties but also to the size and shape of the nanoparticles. The contribution of the longitudinal and transversal modes in gold nanobipyramids is also analyzed in terms of heat generation. These results will guide us to design appropriate nanoparticles to act as efficient heat nanosources.

Janus-Nanojet as an efficient asymmetric photothermal source.

The combination of materials with radically different physical properties in the same nanostructure gives rise to the so-called Janus effects, allowing phenomena of a contrasting nature to occur in the same architecture. Interesting advantages can be taken from a thermal Janus effect for photoinduced hyperthermia cancer therapies. Such therapies have limitations associated to the heating control in terms of temperature stability and energy management. Single-material plasmonic nanoheaters have been widely used for cancer therapies, however, they are highly homogeneous sources that heat the surrounding biological medium isotropically, thus equally affecting cancerous and healthy cells. Here, we propose a prototype of a Janus-Nanojet heating unit based on toroidal shaped plasmonic nanoparticles able to efficiently generate and release local heat directionally under typical unpolarized illumination. Based on thermoplasmonic numerical calculations, we demonstrate that these Janus-based nanoheaters possess superior photothermal conversion features (up to [Formula: see text] K) and unique directional heating capacity, being able to channel up over 90% of the total thermal energy onto a target. We discuss the relevance of these innovative nanoheaters in thermoplasmonics, and hyperthermia cancer therapies, which motivate the development of fabrication techniques for nanomaterials.

Thermophoresis and thermal orientation of Janus nanoparticles in thermal fields.

Thermal fields provide a route to control the motion of nanoparticles and molecules and potentially modify the behaviour of soft matter systems. Janus nanoparticles have emerged as versatile building blocks for the self-assembly of materials with novel properties. Here we investigate using non-equilibrium molecular dynamics simulations the behaviour of coarse-grained models of Janus nanoparticles under thermal fields. We examine the role of the heterogeneous structure of the particle on the Soret coefficient and thermal orientation by studying particles with different internal structures, mass distribution, and particle-solvent interactions. We also examine the thermophoretic response with temperature, targeting liquid and supercritical states and near-critical conditions. We find evidence for a significant enhancement of the Soret coefficient near the critical point, leading to the complete alignment of a Janus particle in the thermal field. This behaviour can be modelled and rationalized using a theory that describes the thermal orientation with the nanoparticle Soret coefficient, the mass and interaction anisotropy of the Janus nanoparticle, and the thermal field's strength. Our simulations show that the mass anisotropy plays a crucial role in driving the thermal orientation of the Janus nanoparticles.

Enhanced Thermo-optical Response by Means of Anapole Excitation.

High refractive index (HRI) dielectric nanostructures offer a versatile platform to control the light-matter interaction at the nanoscale as they can easily support electric and magnetic modes with low losses. An additional property that makes them extraordinary is that they can support low radiative modes, so-called anapole modes. In this work, we propose a spectrally tunable anapole nanoheater based on the use of a dielectric anapole resonator. We show that a gold ring nanostructure, a priori nonresonant, can be turned into a resonant unit by just filling its hole with an HRI material supporting anapole modes, resulting in a more efficient nanoheater able to amplify the photothermal response of the bare nanoring. As proof of concept, we perform a detailed study of the thermoplasmonic response of a gold nanoring used as heating source and a silicon disk, designed to support anapole modes, located in its center acting as an anapolar resonator. Furthermore, we utilize the anapole excitation to easily shift the thermal response of these structures from the shortwave infrared range to the near-infrared range.

Gold nanodoughnut as an outstanding nanoheater for photothermal applications.

Photoinduced hyperthermia is a cancer therapy technique that induces death to cancerous cells via heat generated by plasmonic nanoparticles. While previous studies have shown that some nanoparticles can be effective at killing cancer cells under certain conditions, there is still a necessity (or the need) to improve its heating efficiency. In this work, we perform a detailed theoretical study comparing the thermoplasmonic response of the most effective nanoparticle geometries up to now with a doughnut-shaped nanoparticle. We numerically demonstrate that the latter exhibits a superior tunable photothermal response in practical illumination conditions (unpolarized light). Furthermore, we show that nanoparticle heating in fluidic environments, i.e., nanoparticles undergoing Brownian rotations, strongly depends on the particle orientation with respect to the illumination source. We conclude that nanodoughnuts are the best nanoheaters in our set of structures, with an average temperature increment 40% higher than the second best nanoheater (nanodisk). Furthermore, nanodoughnuts feature a weak dependence on orientation, being therefore ideal candidates for photothermal therapy applications. Finally, we present a designing guide, covering a wide range of toroid designs, which can help on its experimental implementation.

Spatial Control of Heat Flow at the Nanoscale Using Janus Particles.

Janus nanoparticles (JNPs) feature heterogeneous compositions, bringing opportunities in technological and medical applications. We introduce a theoretical approach based on nonequilibrium molecular dynamics simulations and heat transfer continuum theory to investigate the temperature fields generated around heated spherical JNPs covering a wide range of particle sizes, from a few nm to 100 nm. We assess the performance of these nanoparticles to generate anisotropic heating at the nanoscale. We demonstrate that the contrasting interfacial thermal conductances of the fluid-material interfaces arising from the heterogeneous composition of the JNPs can be exploited to control the thermal fields around the nanoparticle, leading to a temperature difference between both sides of the nanoparticle (temperature contrast) that is significant for particles comprising regions with disparate hydrophilicity. We illustrate this idea using coarse-grained and atomistic models of gold nanoparticles with hydrophobic and hydrophilic coatings, in water. Furthermore, we introduce a continuum model to predict the temperature contrast as a function of the interfacial thermal conductance and nanoparticle size. We further show that, unlike homogeneous nanoparticles, the interfacial fluid temperature depends on the interfacial thermal conductance of Janus nanoparticles.

Broadband Unidirectional Forward Scattering with High Refractive Index Nanostructures: Application in Solar Cells.

High refractive index dielectric (HRID) nanoparticles are a clear alternative to metals in nanophotonic applications due to their low losses and directional scattering properties. It has been demonstrated that HRID dimers are more efficient scattering units than single nanoparticles in redirecting the incident radiation towards the forward direction. This effect was recently reported and is known as the "near zero-backward" scattering condition, attained when nanoparticles forming dimers strongly interact with each other. Here, we analyzed the electromagnetic response of HRID isolated nanoparticles and aggregates when deposited on monolayer and graded-index multilayer dielectric substrates. In particular, we studied the fraction of radiation that is scattered towards a substrate with known optical properties when the nanoparticles are located on its surface. We demonstrated that HRID dimers can increase the radiation emitted towards the substrate compared to that of isolated nanoparticles. However, this effect was only present for low values of the substrate refractive index. With the aim of observing the same effect for silicon substrates, we show that it is necessary to use a multilayer antireflection coating. We conclude that dimers of HRID nanoparticles on a graded-index multilayer substrate can increase the radiation scattered into a silicon photovoltaic wafer. The results in this work can be applied to the design of novel solar cells.

On the performance of a tunable grating-based high sensitivity unidirectional plasmonic sensor.

Optical biosensing is currently an intensively active research area, with an increasing demand of highly selective, sensitivity-enhanced and low-cost devices where different plasmonic approaches have been developed. In this work we propose a tunable optimized grating-based gold metasurface that can act both as a high sensitivity sensor device (up to 1500 nm/RIU) and as an unidirectional plasmon source. The theory behind surface plasmon polariton generation is recalled to thoroughly understand the influence that every parameter of the grating source has on the performance of the proposed device. The results and conclusions discussed here offer a key step toward the design of biosensors based on excitation of surface plasmons polaritons by grating-based structures or in the process of creating new nanophotonic circuit devices.

Polarization of acetonitrile under thermal fields via non-equilibrium molecular dynamics simulations.

We show that thermal gradients polarize liquid and supercritical acetonitrile. The polarization results in a stationary electrostatic potential that builds up between hot and cold regions. The strength of the field increases with the static dielectric constant or with decreasing temperature. At near standard conditions, the thermal polarization coefficient is ∼-0.6 mV/K, making it possible to induce significant electrostatic fields, ∼103 V/m, with thermal gradients ∼1 K/µm. At supercritical conditions, ∼600 K and 0.249 g/cm3 (the critical isochore), the electrostatic field is of the same order, despite the low dielectric constant of the fluid. In this case, the electrostatic field is determined by the enhanced rotational diffusion of the molecules and stronger cross-coupling between heat and polarization fluxes. We show that the coupling between the heat and polarization fluxes influences the thermal conductivity of acetonitrile, which becomes a worse heat conductor. For the thermodynamic states investigated in this work, the thermal polarization effect leads to a ∼2%-5% reduction in thermal conductivity.

Plasmonic linear nanomotor using lateral optical forces.

Optical force is a powerful tool to actuate micromachines. Conventional approaches often require focusing and steering an incident laser beam, resulting in a bottleneck for the integration of the optically actuated machines. Here, we propose a linear nanomotor based on a plasmonic particle that generates, even when illuminated with a plane wave, a lateral optical force due to its directional side scattering. This force direction is determined by the orientation of the nanoparticle rather than a field gradient or propagation direction of the incident light. We demonstrate the arrangements of the particles allow controlling the lateral force distributions with the resolution beyond the diffraction limit, which can produce movements, as designed, of microobjects in which they are embedded without shaping and steering the laser beam. Our nanomotor to engineer the experienced force can open the door to a new class of micro/nanomechanical devices that can be entirely operated by light.

All-Dielectric Chiral Metasurfaces Based on Crossed-Bowtie Nanoantennas.

Circular dichroism spectroscopy is a technique used to discriminate molecular chirality, which is essential in fields like biology, chemistry, or pharmacology where different chiral agents often show different biological activities. Nevertheless, due to the inherently weak molecular-chiroptical activity, this technique is limited to high concentrations or large analyte volumes. Finding novel ways to enhance the circular dichroism would boost the performance of these techniques. So far, the enhancement of light-matter interaction mediated by plasmons is the most common way to develop chiral plasmonic structures with extraordinarily strong chiroptical responses. However, absorptive losses of metals at optical frequencies has hindered its practical use in many scenarios. In this work, we propose an all-dielectric low-loss chiral metasurface with unit cells built by high-refractive-index crossed-bowtie nanoantennas. These unit cells, built of silicon, strongly increase the chiroptical effect through the simultaneous interaction of their electric and magnetic modes, which in contrast to other recent proposals shows at the same time a high concentration of the electric field in its gap that leads to the presence of hotspots. The proposed structure exhibits a circular dichroism spectra up to 3-fold higher than that of previous proposals that use complex plasmonic or hybrid nanostructures, making it a clear alternative to develop low-loss metasurfaces with potential applications in chiral target sensing/biosensing. For completeness, single triangular shaped and symmetric (achiral) bowtie nanostructures were also studied as possible candidates for a detection up to the single-molecule level due the lack of a circular dichroism background of the nanostructures themselves.

Understanding and Reducing Photothermal Forces for the Fabrication of Au Nanoparticle Dimers by Optical Printing.

Optical printing holds great potential to enable the use of the vast variety of colloidal nanoparticles (NPs) in nano- and microdevices and circuits. By means of optical forces, it enables the direct assembly of NPs, one by one, onto specific positions of solid surfaces with great flexibility of pattern design and no need of previous surface patterning. However, for unclear causes it was not possible to print identical NPs closer to each other than 300 nm. Here, we show that the repulsion restricting the optical printing of close by NPs arises from light absorption by the printed NPs and subsequent local heating. By optimizing heat dissipation, it is possible to reduce the minimum separation between NPs. Using a reduced graphene oxide layer on a sapphire substrate, we demonstrate for the first time the optical printing of Au-Au NP dimers. Modeling the experiments considering optical, thermophoretic, and thermo-osmotic forces we obtain a detailed understanding and a clear pathway for the optical printing fabrication of complex nano structures and circuits based on connected colloidal NPs.

Efficient Third Harmonic Generation from Metal-Dielectric Hybrid Nanoantennas.

High refractive index dielectric nanoantennas are expected to become key elements for nonlinear nano-optics applications due to their large nonlinearities, low energy losses, and ability to produce high electric field enhancements in relatively large nanoscale volumes. In this work, we show that the nonlinear response from a high-index dielectric nanoantenna can be significantly improved by adding a metallic component to build a metal-dielectric hybrid nanostructure. We demonstrate that the plasmonic resonance of a Au nanoring can boost the anapole mode supported by a Si nanodisk, strongly enhancing the electric field inside the large third-order susceptibility dielectric. As a result, a high third harmonic conversion efficiency, which reaches 0.007% at a third harmonic wavelength of 440 nm, is obtained. In addition, by suitably modifying geometrical parameters of the hybrid nanoantenna, we tune the enhanced third harmonic emission throughout the optical regime. Coupling metallic and dielectric nanoantennas to expand the potential of subwavelength structures opens new paths for efficient nonlinear optical effects in the visible range on the nanoscale.

Enhanced Transverse Magneto-Optical Kerr Effect in Magnetoplasmonic Crystals for the Design of Highly Sensitive Plasmonic (Bio)sensing Platforms.

We propose a highly sensitive sensor based on enhancing the transversal magneto-optical Kerr effect (TMOKE) through excitation of surface plasmon resonances in a novel and simple architecture, which consists of a metal grating on a metal magneto-optical layer. Detection of the change in the refractive index of the analyte medium is made by monitoring the angular shift of the Fano-like resonances associated with TMOKE. A higher resolution is obtained with this technique than with reflectance curves. The key aspect of the novel architecture is to achieve excitation of surface plasmon resonances mainly localized at the sensing layer, where interaction with the analyte occurs. This led to a high sensitivity, S = 190° RIU-1, and high performance with a figure of merit of the order of 103, which can be exploited in sensors and biosensors.

Unidirectional light scattering with high efficiency at optical frequencies based on low-loss dielectric nanoantennas.

Dielectric nanoparticles offer low optical losses and access to both electric and magnetic Mie resonances. This enables unidirectional scattering along the incident axis of light, owing to the interference between these two resonances. Here we theoretically and experimentally demonstrate that an asymmetric dimer of dielectric nanoparticles can provide unidirectional forward scattering with high efficiency. Theoretical analyses reveal that the dimer configuration can satisfy the first Kerker condition at the resonant peaks of electric and magnetic dipolar modes, therefore showing highly efficient directional forward scattering. The unidirectional forward scattering with high efficiency is confirmed in our experiments using a silicon nanodisk dimer on a transparent substrate. This study will boost the realization of practical applications using low-loss and efficient subwavelength all-dielectric nanoantennas.

Tailored Hypersound Generation in Single Plasmonic Nanoantennas.

Ultrashort laser pulses impinging on a plasmonic nanostructure trigger a highly dynamic scenario in the interplay of electronic relaxation with lattice vibrations, which can be experimentally probed via the generation of coherent phonons. In this Letter, we present studies of hypersound generation in the range of a few to tens of gigahertz on single gold plasmonic nanoantennas, which have additionally been subjected to predesigned mechanical constraints via silica bridges. Using these hybrid gold/silica nanoantennas, we demonstrate experimentally and via numerical simulations how mechanical constraints allow control over their vibrational mode spectrum. Degenerate pump-probe techniques with double modulation are performed in order to detect the small changes produced in the probe transmission by the mechanical oscillations of these single nanoantennas.

Switchable directional scattering of electromagnetic radiation with subwavelength asymmetric silicon dimers.

High refractive index dielectric nanoparticles show high promise as a complementary nanophotonics platform due to compared with plasmonic nanostructures low absorption losses and the co-existence of magnetic and electric resonances. Here we explore their use as resonantly enhanced directional scatterers. We theoretically demonstrate that an asymmetric dimer of silicon nanoparticles shows tuneable directional scattering depending on the frequency of excitation. This is due to the interference between electric and magnetic dipoles excited in each nanoparticle, enabling directional control of the scattered light. Interestingly, this control can be achieved regardless of the polarization direction with respect to the dimer axis; however, difference in the polarization can shift the wavelengths at which the directional scattering is achieved. We also explore the application of such an asymmetric nanoantenna as a tuneable routing element in a nanometer scale, suggesting applications in optical nanocircuitry.

Non-plasmonic nanoantennas for surface enhanced spectroscopies with ultra-low heat conversion.

Nanoplasmonics has recently revolutionized our ability to control light on the nanoscale. Using metallic nanostructures with tailored shapes, it is possible to efficiently focus light into nanoscale field 'hot spots'. High field enhancement factors have been achieved in such optical nanoantennas, enabling transformative science in the areas of single molecule interactions, highly enhanced nonlinearities and nanoscale waveguiding. Unfortunately, these large enhancements come at the price of high optical losses due to absorption in the metal, severely limiting real-world applications. Via the realization of a novel nanophotonic platform based on dielectric nanostructures to form efficient nanoantennas with ultra-low light-into-heat conversion, here we demonstrate an approach that overcomes these limitations. We show that dimer-like silicon-based single nanoantennas produce both high surface enhanced fluorescence and surface enhanced Raman scattering, while at the same time generating a negligible temperature increase in their hot spots and surrounding environments.

Plasmonic control of radiative properties of semiconductor quantum dots coupled to plasmonic ring cavities.

In recent years, a lot of effort has been made to achieve controlled delivery of target particles to the hotspots of plasmonic nanoantennas, in order to probe and/or exploit the extremely large field enhancements produced by such structures. While in many cases such high fields are advantageous, there are instances where they should be avoided. In this work, we consider the implications of using the standard nanoantenna geometries when colloidal quantum dots are employed as target entities. We show that in this case, and for various reasons, dimer antennas are not the optimum choice. Plasmonic ring cavities are a better option despite low field enhancements, as they allow collective coupling of many quantum dots in a reproducible and predictable manner. In cases where larger field enhancements are required, or for larger quantum dots, nonconcentric ring-disk cavities can be employed instead.