Pietro G. Gucciardi

Optical trapping and manipulation of nanostructures

Optical trapping and manipulation of micrometre-sized particles was first reported in 1970. Since then, it has been successfully implemented in two size ranges: the subnanometre scale, where light-matter mechanical coupling enables cooling of atoms, ions and molecules, and the micrometre scale, where the momentum transfer resulting from light scattering allows manipulation of microscopic objects such as cells. But it has been difficult to apply these techniques to the intermediate - nanoscale - range that includes structures such as quantum dots, nanowires, nanotubes, graphene and two-dimensional crystals, all of crucial importance for nanomaterials-based applications. Recently, however, several new approaches have been developed and demonstrated for trapping plasmonic nanoparticles, semiconductor nanowires and carbon nanostructures. Here we review the state-of-the-art in optical trapping at the nanoscale, with an emphasis on some of the most promising advances, such as controlled manipulation and assembly of individual and multiple nanostructures, force measurement with femtonewton resolution, and biosensors.

Brownian Motion of Graphene

Brownian motion is a manifestation of the fluctuation-dissipation theorem of statistical mechanics. It regulates systems in physics, biology, chemistry, and finance. We use graphene as prototype material to unravel the consequences of the fluctuation-dissipation theorem in two dimensions, by studying the Brownian motion of optically trapped graphene flakes. These orient orthogonal to the light polarization, due to the optical constants anisotropy. We explain the flake dynamics in the optical trap and measure force and torque constants from the correlation functions of the tracking signals, as well as comparing experiments with a full electromagnetic theory of optical trapping. The understanding of optical trapping of two-dimensional nanostructures gained through our Brownian motion analysis paves the way to light-controlled manipulation and all-optical sorting of biological membranes and anisotropic macromolecules.

Optical Nanoantennas for Multiband Surface-Enhanced Infrared and Raman Spectroscopy

In this article we show that linear nanoantennas can be used as shared substrates for surface-enhanced Raman and infrared spectroscopy (SERS and SEIRS, respectively). This is done by engineering the plasmonic properties of the nanoantennas, so to make them resonant in both the visible (transversal resonance) and the infrared (longitudinal resonance), and by rotating the excitation field polarization to selectively take advantage of each resonance and achieve SERS and SEIRS on the same nanoantennas. As a proof of concept, we have fabricated gold nanoantennas by electron beam lithography on calcium difluoride (1-2 μm long, 60 nm wide, 60 nm high) that exhibit a transverse plasmonic resonance in the visible (640 nm) and a particularly strong longitudinal dipolar resonance in the infrared (tunable in the 1280-3100 cm(-1) energy range as a function of the length). SERS and SEIRS detection of methylene blue molecules adsorbed on the nanoantennas surface is accomplished, with signal enhancement factors of 5×10(2) for SERS (electromagnetic enhancement) and up to 10(5) for SEIRS. Notably, we find that the field enhancement provided by the transverse resonance is sufficient to achieve SERS from single nanoantennas. Furthermore, we show that by properly tuning the nanoantenna length the signals of a multitude of vibrational modes can be enhanced with SEIRS. This simple concept of plasmonic nanosensor is highly suitable for integration on lab-on-a-chip schemes for label-free chemical and biomolecular identification with optimized performances.

FemtoNewton force sensing with optically trapped nanotubes

We extract the distribution of both center-of-mass and angular fluctuations from three-dimensional tracking of optically trapped nanotubes. We measure the optical force and torque constants from autocorrelation and cross-correlation of the tracking signals. This allows us to isolate the angular Brownian motion. We demonstrate that nanotubes enable nanometer spatial and femtonewton force resolution in photonic force microscopy, the smallest to date. This has wide implications in nanotechnology, biotechnology, nanofluidics, and material science.

Re-radiation Enhancement in Polarized Surface-Enhanced Resonant Raman Scattering of Randomly Oriented Molecules on Self-Organized Gold Nanowires

We explore the effect of re-radiation in surface-enhanced Raman scattering (SERS) through polarization-sensitive experiments on self-organized gold nanowires on which randomly oriented Methylene Blue molecules are adsorbed. We provide the exact laws ruling the polarized, unpolarized, and parallel- and cross-polarized SERS intensity as a function of the field polarizations. We show that SERS is polarized along the wire-to-wire nanocavity axis, independently from the excitation polarization. This proves the selective enhancement of the Raman dipole component parallel to the nanocavity at the single molecule level. Introducing a field enhancement tensor to account for the anisotropic polarization response of the nanowires, we work out a model that correctly predicts the experimental results for any excitation/detection polarization and goes beyond the E(4) approximation. We also show how polarization-sensitive SERS experiments permit one to evaluate independently the excitation and the re-radiation enhancement factors accessing the orientation-averaged non-diagonal components of the molecular Raman polarizability tensor.

Rotation Detection in Light-Driven Nanorotors

We analyze the rotational dynamics of light driven nanorotors, made of nanotube bundles and gold nanorods aggregates, with nonsymmetric shapes, trapped in optical tweezers. We identify two different regimes depending on dimensions and optical properties of the nanostructures. These correspond to alignment with either the laser propagation axis or the dominant polarization direction, or rotational motions caused by either unbalanced radiation pressure or polarization torque. By analyzing the motion correlations of the trapped nanostructures, we measure with high accuracy both the optical trapping parameters and the rotation frequency induced by the radiation pressure. Our results pave the way to improved all-optical detection, control over rotating nanomachines, and rotation detection in nano-optomechanics.

Plasmon-enhanced optical trapping of gold nanoaggregates with selected optical properties.

We show how light forces can be used to trap gold nanoaggregates of selected structure and optical properties obtained by laser ablation in liquid. We measure the optical trapping forces on nanoaggregates with an average size range 20-750 nm, revealing how the plasmon-enhanced fields play a crucial role in the trapping of metal clusters featuring different extinction properties. Force constants of the order of 10 pN/nmW are detected, the highest measured on a metal nanostructure. Finally, by extending the transition matrix formalism of light scattering theory to the optical trapping of metal nanoaggregates, we show how the plasmon resonances and the fractal structure arising from aggregation are responsible for the increased forces and wider trapping size range with respect to individual metal nanoparticles.

Size-scaling in optical trapping of silicon nanowires.

We investigate size-scaling in optical trapping of ultrathin silicon nanowires showing how length regulates their Brownian dynamics, optical forces, and torques. Force and torque constants are measured on nanowires of different lengths through correlation function analysis of their tracking signals. Results are compared with a full electromagnetic theory of optical trapping developed in the transition matrix framework, finding good agreement.

Single wall carbon nanotubes deposited on stainless steel sheet substrates as novel counter electrodes for ruthenium polypyridine based dye sensitized solar cells

We report on the implementation of stainless steel foils coated with dispersed Single Wall Carbon Nanotubes as novel, low cost and highly efficient counter electrodes for dye sensitized solar cells (DSSCs). We use commercially available non purified nanotubes dispersed in water by ultrasonication and drop cast on stainless steel substrates. When implemented on a ruthenium based DSSC we obtain a high short circuit current density (J(sc)= 9.21 mA cm(-2)), a good open circuit voltage (V(oc) = 0.660 V) and a solar energy conversion efficiency of 3.92%. The above cited values are measured under a light flux of 100 mW cm(-2) generated by a solar simulator equipped with a filter AM 1.5. The obtained results are comparable to those attained using a stainless steel counter electrode sputtered with a 2 microm thick platinum film (J(sc) 10.92 mA cm(-2), V(max) = 0.66 V and eta = 4.5%, AM 1.5).

Optical trapping of nanotubes with cylindrical vector beams

We use laser beams with radial and azimuthal polarization to optically trap carbon nanotubes. We measure force constants and trap parameters as a function of power showing improved axial trapping efficiency with respect to linearly polarized beams. The analysis of the thermal fluctuations highlights a significant change in the optical trapping potential when using cylindrical vector beams. This enables the use of polarization states to shape optical traps according to the particle geometry, as well as paving the way to nanoprobe-based photonic force microscopy with increased performance compared to a standard linearly polarized configuration.