Synthesis and Raman Detection of 5-Amino-2-mercaptobenzimidazole Self-Assembled Monolayers in Nanoparticle-on-a-Mirror Plasmonic Cavity Driven by Dielectric Waveguides.

Functionalization of metallic surfaces by molecular monolayers is a key process in fields such as nanophotonics or biotechnology. To strongly enhance light-matter interaction in such monolayers, nanoparticle-on-a-mirror (NPoM) cavities can be formed by placing metal nanoparticles on such chemically functionalized metallic monolayers. In this work, we present a novel functionalization process of gold surfaces using 5-amino-2-mercaptobenzimidazole (5-A-2MBI) molecules, which can be used for upconversion from THz to visible frequencies. The synthesized surfaces and NPoM cavities are characterized by Raman spectroscopy, atomic force microscopy (AFM), and advancing-receding contact angle measurements. Moreover, we show that NPoM cavities can be efficiently integrated on a silicon-based photonic chip performing pump injection and Raman-signal extraction via silicon nitride waveguides. Our results open the way for the use of 5-A-2MBI monolayers in different applications, showing that NPoM cavities can be effectively integrated with photonic waveguides, enabling on-chip enhanced Raman spectroscopy or detection of infrared and THz radiation.

Accurate Transfer of Individual Nanoparticles onto Single Photonic Nanostructures.

Controlled integration of metallic nanoparticles (NPs) onto photonic nanostructures enables the realization of complex devices for extreme light confinement and enhanced light-matter interaction. For instance, such NPs could be massively integrated on metal plates to build nanoparticle-on-mirror (NPoM) nanocavities or photonic integrated waveguides (WGs) to build WG-driven nanoantennas. However, metallic NPs are usually deposited via drop-casting, which prevents their accurate positioning. Here, we present a methodology for precise transfer and positioning of individual NPs onto different photonic nanostructures. Our method is based on soft lithography printing that employs elastomeric stamp-assisted transfer of individual NPs onto a single nanostructure. It can also parallel imprint many individual NPs with high throughput and accuracy in a single step. Raman spectroscopy confirms enhanced light-matter interactions in the resulting NPoM-based nanophotonic devices. Our method mixes top-down and bottom-up nanofabrication techniques and shows the potential of building complex photonic nanodevices for multiple applications ranging from enhanced sensing and spectroscopy to signal processing.

Radiationless anapole states in on-chip photonics.

High-index nanoparticles are known to support radiationless states called anapoles, where dipolar and toroidal moments interfere to inhibit scattering to the far field. In order to exploit the striking properties arising from these interference conditions in photonic integrated circuits, the particles must be driven in-plane via integrated waveguides. Here, we address the excitation of electric anapole states in silicon disks when excited on-chip at telecom wavelengths. In contrast to normal illumination, we find that the anapole condition-identified by a strong reduction of the scattering-does not overlap with the near-field energy maximum, an observation attributed to retardation effects. We experimentally verify the two distinct spectral regions in individual disks illuminated in-plane from closely placed waveguide terminations via far-field and near-field measurements. Our finding has important consequences concerning the use of anapole states and interference effects of other Mie-type resonances in high-index nanoparticles for building complex photonic integrated circuitry.

Mirror effect in atomic force microscopy profiles enables tip reconstruction.

In this work, the tip convolution effect in atomic force microscopy is revisited to illustrate the capabilities of cubic objects for determination of the tip shape and size. Using molecular-based cubic nanoparticles as a reference, a two-step tip reconstruction process has been developed. First, the tip-to-face angle is estimated by means of an analysis of the convolution error while the tip radius is extracted from the experimental profiles. The results obtained are in good agreement with specification of the tip supplier even though the experiments have been conducted using real distribution of nanoparticles with dispersion in size and aspect ratio. This demonstrates the reliability of our method and opens the door for a more accurate tip reconstruction by using calibration standards.

Green and Sustainable Manufacture of Ultrapure Engineered Nanomaterials.

Nanomaterials with very specific features (purity, colloidal stability, composition, size, shape, location…) are commonly requested by cutting-edge technologic applications, and hence a sustainable process for the mass-production of tunable/engineered nanomaterials would be desirable. Despite this, tuning nano-scale features when scaling-up the production of nanoparticles/nanomaterials has been considered the main technological barrier for the development of nanotechnology. Aimed at overcoming these challenging frontier, a new gas-phase reactor design providing a shorter residence time, and thus a faster quenching of nanoclusters growth, is proposed for the green, sustainable, versatile, cost-effective, and scalable manufacture of ultrapure engineered nanomaterials (ranging from nanoclusters and nanoalloys to engineered nanostructures) with a tunable degree of agglomeration, composition, size, shape, and location. This method enables: (1) more homogeneous, non-agglomerated ultrapure Au-Ag nanoalloys under 10 nm; (2) 3-nm non-agglomerated ultrapure Au nanoclusters with lower gas flow rates; (3) shape-controlled Ag NPs; and (4) stable Au and Ag engineered nanostructures: nanodisks, nanocrosses, and 3D nanopillars. In conclusion, this new approach paves the way for the green and sustainable mass-production of ultrapure engineered nanomaterials.

Contact damage of human dental enamel under cyclic axial loading with abrasive particles.

The damage to human dental enamel under cyclic, axial contacts in a silica particle medium is investigated. It is found that such damage is hierarchical, affecting different length-scales of the enamel structure. At the contact surface, it consists of micron-sized defects, with an attendant increase of surface roughness due to microindentation of the abrasive particles. Below the surface, demineralization of the enamel is observed, which is attributable to inelastic processes at the nanoscale. Axial-only contacts in particulate media result in negligible wear at the macroscopic scale, but may degrade the fracture strength. Potential implications of these results in the fields of dentistry and biology are discussed.

Experimental study of an evanescent-field biosensor based on 1D photonic bandgap structures.

A photonic bandgap (PBG) biosensor has been developed for the label-free detection of proteins. As the sensing in this type of structures is governed by the interaction between the evanescent field going into the cladding and the target analytes, scanning near-field optical microscopy has been used to characterize the profile of that evanescent field. The study confirms the strong exponential decrease of the signal as it goes into the cladding. This means that biorecognition events must occur as close to the PBG structure surface as possible in order to obtain the maximum sensing response. Within this context, the PBG biosensor has been biofunctionalized with half-antibodies specific to bovine serum albumin (BSA) using a UV-induced immobilization procedure. The use of half-antibodies allows one to reduce the thickness of the biorecognition volume down to ca. 2.5 nm, thus leading to a higher interaction with the evanescent field, as well as a proper orientation of their binding sites towards the target sample. Then, the biofunctionalized PBG biosensor has been used to perform a direct and real-time detection of the target BSA antigen.

Enhanced superconductivity in atomically thin TaS2.

The ability to exfoliate layered materials down to the single layer limit has presented the opportunity to understand how a gradual reduction in dimensionality affects the properties of bulk materials. Here we use this top-down approach to address the problem of superconductivity in the two-dimensional limit. The transport properties of electronic devices based on 2H tantalum disulfide flakes of different thicknesses are presented. We observe that superconductivity persists down to the thinnest layer investigated (3.5 nm), and interestingly, we find a pronounced enhancement in the critical temperature from 0.5 to 2.2 K as the layers are thinned down. In addition, we propose a tight-binding model, which allows us to attribute this phenomenon to an enhancement of the effective electron-phonon coupling constant. This work provides evidence that reducing the dimensionality can strengthen superconductivity as opposed to the weakening effect that has been reported in other 2D materials so far.

Switching the Magnetic Vortex Core in a Single Nanoparticle.

Imaging and manipulating the spin structure of nano- and mesoscale magnetic systems is a challenging topic in magnetism, yielding a wide range of spin phenomena such as skyrmions, hedgehog-like spin structures, or vortices. A key example has been provided by the vortex spin texture, which can be addressed in four independent states of magnetization, enabling the development of multibit magnetic storage media. Most of the works devoted to the study of the magnetization reversal mechanisms of the magnetic vortices have been focused on micrometer-size magnetic platelets. Here we report the experimental observation of the vortex state formation and annihilation in individual 25 nm molecular-based magnetic nanoparticles measured by low-temperature variable-field magnetic force microscopy. Interestingly, in these nanoparticles the switching of the vortex core can be induced with very small values of the applied static magnetic field.

Current rectification in a single molecule diode: the role of electrode coupling.

We demonstrate large rectification ratios (> 100) in single-molecule junctions based on a metal-oxide cluster (polyoxometalate), using a scanning tunneling microscope (STM) both at ambient conditions and at low temperature. These rectification ratios are the largest ever observed in a single-molecule junction, and in addition these junctions sustain current densities larger than 10(5) A cm(-2). By following the variation of the I-V characteristics with tip-molecule separation we demonstrate unambiguously that rectification is due to asymmetric coupling to the electrodes of a molecule with an asymmetric level structure. This mechanism can be implemented in other type of molecular junctions using both organic and inorganic molecules and provides a simple strategy for the rational design of molecular diodes.

Correction of the tip convolution effects in the imaging of nanostructures studied through scanning force microscopy.

AFM images are always affected by artifacts arising from tip convolution effects, resulting in a decrease in the lateral resolution of this technique. The magnitude of such effects is described by means of geometrical considerations, thereby providing better understanding of the convolution phenomenon. We demonstrate that for a constant tip radius, the convolution error is increased with the object height, mainly for the narrowest motifs. Certain influence of the object shape is observed between rectangular and elliptical objects with the same height. Such moderate differences are essentially expected among elongated objects; in contrast they are reduced as the object aspect ratio is increased. Finally, we propose an algorithm to study the influence of the size, shape and aspect ratio of different nanometric motifs on a flat substrate. Indeed, with this algorithm, convolution artifacts can be extended to any kind of motif including real surface roughness. From the simulation results we demonstrate that in most cases the real motif's width can be estimated from AFM images without knowing its shape in detail.

Tuning size and thermal hysteresis in bistable spin crossover nanoparticles.

Nanoparticles of iron(II) triazole salts have been prepared from water-organic microemulsions. The mean size of the nanoparticles can be tuned down to 6 nm in diameter, with a narrow size distribution. A sharp spin transition from the low spin (LS) to the high spin (HS) state is observed above room temperature, with a 30-40-K-wide thermal hysteresis. The same preparation can yield second generation nanoparticles containing molecular alloys by mixing triazole with triazole derivatives, or from metallic mixtures of iron(II) and zinc(II). In these nanoparticles of 10-15 nm, the spin transition "moves" towards lower temperatures, reaching a 316 K limit for the cooling down transition and maintaining a thermal hysteresis over 15-20-K-wide. The nanoparticles were characterized by dynamic light scattering, TEM, and AFM, after deposition on gold or silicon surfaces. The spin transition was characterized by magnetic susceptibility measurements and EXAFS (in solid samples after solvent removal) and also by the color change between the LS (violet) and HS (colorless) states in an organic solvent suspension. The discovery of bistable magnetic nanoparticles of 6 nm with a wide thermal hysteresis above room temperature showcases the actual possibilities of spin crossover materials for nanotechnological applications.