No Arabic abstract
The applications of plasmonics to energy transfer from free-space radiation to molecules are currently limited to the visible region of the electromagnetic spectrum due to the intrinsic optical properties of bulk noble metals that support strong electromagnetic field confinement only close to their plasma frequency in the visible/ultraviolet range. In this work, we show that nanoporous gold can be exploited as plasmonic material for the mid-infrared region to obtain strong electromagnetic field confinement, co-localized with target molecules into the nanopores and resonant with their vibrational frequency. The effective optical response of the nanoporous metal enables the penetration of optical fields deep into the nanopores, where molecules can be loaded thus achieving a more efficient light-matter coupling if compared to bulk gold. In order to realize plasmonic resonators made of nanoporous gold, we develop a nanofabrication method based on polymeric templates for metal deposition and we obtain antenna arrays resonating at mid-infrared wavelengths selected by design. We then coat the antennas with a thin (3 nm) silica layer acting as target dielectric layer for optical energy transfer. We study the strength of the light-matter coupling at the vibrational absorption frequency of silica at 1250 cm-1 through the analysis of the experimental Fano lineshape that is benchmarked against identical structures made of bulk gold. The boost of optical energy transfer from free-space mid-infrared radiation to molecular vibrations in nanoporous 3D nanoantenna arrays can open new application routes for plasmon-enhanced physical-chemical reactions.
A robust and reproducible preparation of self-standing nanoporous gold leaves (NPGL) is presented, with optical characterization and plasmonic behaviour analysis. Nanoporous gold (NPG) layers are tipically prepared as thin films on a bulk substrate. Here we present an alternative approach consisting in the preparation of NPGL in the form of a self-standing film. This solution leads to a perfectly symmetric configuration where the metal is immersed in a homogeneous medium and in addition can support the propagation of symmetric and antisymmetric plasmonic modes. With respect to bulk gold, NPG shows metallic behaviour at higher wavelengths, suggesting possible plasmonic applications in the near / medium infrared range. In this work the plasmonic properties in the wide wavelength range from the ultraviolet up to the mid-infrared range have been investigated.
Plasmonics applications have been extending into the ultraviolet region of the electromagnetic spectrum. Unfortunately the commonly used noble metals have intrinsic optical properties that limit their use above 350 nm. Aluminum is probably the most suitable material for UV plasmonics and in this work we show that nanoporous aluminum can be prepared starting from an alloy of Mg3Al2. The porous metal is obtained by means of a galvanic replacement reaction. Such a nanoporous metal can be exploited to achieve a plasmonic material for enhanced UV Raman spectroscopy and fluorescence. Thanks to the large surface to volume ratio this material represents a powerful platform for promoting interaction between plasmonic substrates and molecules in the UV.
Transition metal dichalcogenides have emerged as promising materials for nano-photonic resonators due to their large refractive index, low absorption within the visible spectrum and compatibility with a wide variety of substrates. Here we use these properties to fabricate WS$_2$ monomer and dimer nano-antennas in a variety of geometries enabled by the anisotropy in the crystal structure. Using dark field spectroscopy, we reveal multiple Mie resonances, including anapole modes, for which we show polarization-sensitive second harmonic generation in the dimer nano-antennas. We introduce post-fabrication atomic force microscopy repositioning and rotation of dimer nano-antennas, achieving gaps as small as 10$pm$5 nm and opening a host of potential applications. We further studied these structures with numerical simulations yielding electric field intensity enhancements of >10$^3$ corresponding to Purcell factors as high as 157 for emitters positioned within the nano-antenna hotspots. Optical trapping simulations of small dimer gaps yield attractive forces of >350 fN for colloidal quantum dots and > 70 fN for protein-like, polystyrene beads. Our findings highlight the advantages of using transition metal dichalcogenides for nano-photonics by exploring new applications enabled by their unique properties.
There is a great interest in the scientific community to perform calorimetry on samples having mass in the nanogram range. A detailed knowledge of the energy (heat) exchange in the fast growing family of micro- and nano-systems could provide valuable information about the chemistry and physics at the nano-scale. The possibility to have an atomically flat thermal probe represents an added value, because it provides the unique opportunity to perform Scanning Probe Microscopy (SPM) together with calorimetry. Here we report the fabrication, characterization, and calibration of atomically flat, single-crystalline gold film thermometers on mica substrate. Gold re-crystallization has been obtained, and successively the thermometer surface has been studied by Low Energy Electron Diffraction (LEED) and Scanning Tunneling Microscopy (STM). The thermometer calibration demonstrates a heat exchange coefficient of 2.1 x 10^(-7) W/K and a performance about 10 times better than previous sensors based on Si substrates. The experimental setup allows the simultaneous investigation of heat exchange and surface physics on the same sample.
This work summarizes recent progress on the thermal transport properties of three-dimensional (3D) nanostructures, with an emphasis on experimental results. Depending on the applications, different 3D nanostructures can be prepared or designed to either achieve a low thermal conductivity for thermal insulation or thermoelectric devices, or a high thermal conductivity for thermal interface materials used in the continuing miniaturization of electronics. A broad range of 3D nanostructures have been discussed, ranging from colloidal crystals/assemblies, array structures, holey structures, hierarchical structures, 3D nanostructured fillers for metal matrix composites and polymer composites. Different factors that impact the thermal conductivity of these 3D structures are compared and analyzed. This work provides an overall understanding of the thermal transport properties of various 3D nanostructures, which will shed light on the thermal management at nanoscale.