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.

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.

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.

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.

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.

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.

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.

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.

Precise attoliter temperature control of nanopore sensors using a nanoplasmonic bullseye.

Targeted temperature control in nanopores is greatly important in further understanding biological molecules. Such control would extend the range of examinable molecules and facilitate advanced analysis, including the characterization of temperature-dependent molecule conformations. The work presented within details well-defined plasmonic gold bullseye and silicon nitride nanopore membranes. The bullseye nanoantennae are designed and optimized using simulations and theoretical calculations for interaction with 632.8 nm laser light. Laser heating was monitored experimentally through nanopore conductance measurements. The precise heating of nanopores is demonstrated while minimizing the accumulation of heat in the surrounding membrane material.

Plasmon enhanced fluorescence with aggregated shell-isolated nanoparticles.

Shell-isolated nanoparticles (SHINs) nanostructures provide a versatile substrate where the localized surface plasmon resonances (LSPRs) are well-defined. For SHINEF, the silver (or gold) metal core is protected by the SiO2 coating, which is thicker than the critical distance for minimum quenching by the metal. In the present work, it is shown that an increase in the SHINEF enhancement factor may be achieved by inducing SHIN aggregation with electrolytes in solution. The proof of concept is demonstrated using NaCl as aggregating agent, although other inorganic salts will also aggregate SHIN nanoparticles. As much as a 10-fold enhancement in the SHINEF enhancement factor (EF) may be achieved by tuning the electrolyte concentrations in solution. The SHINEF experiments include the study of the aggregation effect controlling gold SHIN's surface concentration via spraying. Au-SHINs are sprayed onto layer-by-layer (LbL) and Langmuir-Blodgett (LB) films, and samples are fabricated using fluorophores with low and also high quantum yield.

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.

Visualizing the near-field coupling and interference of bonding and anti-bonding modes in infrared dimer nanoantennas.

We directly visualize and identify the capacitive coupling of infrared dimer antennas in the near field by employing scattering-type scanning near-field optical microscopy (s-SNOM). The coupling is identified by (i) resolving the strongly enhanced nano-localized near fields in the antenna gap and by (ii) tracing the red shift of the dimer resonance when compared to the resonance of the single antenna constituents. Furthermore, by modifying the illumination geometry we break the symmetry, providing a means to excite both the bonding and the "dark" anti-bonding modes. By spectrally matching both modes, their interference yields an enhancement or suppression of the near fields at specific locations, which could be useful in nanoscale coherent control applications.

Detection of deep-subwavelength dielectric layers at terahertz frequencies using semiconductor plasmonic resonators.

Plasmonic bowtie antennas made of doped silicon can operate as plasmonic resonators at terahertz (THz) frequencies and provide large field enhancement close to their gap. We demonstrate both experimentally and theoretically that the field confinement close to the surface of the antenna enables the detection of ultrathin (100 nm) inorganic films, about 3750 times thinner than the free space wavelength. Based on model calculations, we conclude that the detection sensitivity and its variation with the thickness of the deposited layer are related to both the decay of the local THz field profile around the antenna and the local field enhancement in the gap of the bowtie antenna. This large field enhancement has the potential to improve the detection limits of plasmon-based biological and chemical sensors.

All-optical control of a single plasmonic nanoantenna-ITO hybrid.

We demonstrate experimentally picosecond all-optical control of a single plasmonic nanoantenna embedded in indium tin oxide (ITO). We identify a picosecond response of the antenna-ITO hybrid system, which is distinctly different from transient bleaching observed for gold antennas on a nonconducting SiO(2) substrate. Our experimental results can be explained by the large free-carrier nonlinearity of ITO, which is enhanced by plasmon-induced hot-electron injection from the gold nanoantenna into the conductive oxide. The combination of tunable antenna-ITO hybrids with nanoscale plasmonic energy transfer mechanisms, as demonstrated here, opens a path for new ultrafast devices to produce nanoplasmonic switching and control.

Real-space mapping of Fano interference in plasmonic metamolecules.

An unprecedented control of the spectral response of plasmonic nanoantennas has recently been achieved by designing structures that exhibit Fano resonances. This new insight is paving the way for a variety of applications, such as biochemical sensing and surface-enhanced Raman spectroscopy. Here we use scattering-type near-field optical microscopy to map the spatial field distribution of Fano modes in infrared plasmonic systems. We observe in real space the interference of narrow (dark) and broad (bright) plasmonic resonances, yielding intensity and phase toggling between different portions of the plasmonic metamolecules when either their geometric sizes or the illumination wavelength is varied.

Shape matters: plasmonic nanoparticle shape enhances interaction with dielectric substrate.

Numerical analyses of the ultraviolet and visible plasmonic spectra measured from hemispherical gallium nanostructures on dielectric substrates reveal that resonance frequencies are quite sensitive to illumination angle and polarization in a way that depends on nanostructure size, shape, and substrate. Large, polarization-dependent splittings arise from the broken symmetry of hemispherical gallium nanoparticles on sapphire substrates, inducing strong interactions with the substrate that depend sensitively on the angle of illumination and the nanoparticle diameter.

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.

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.

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.