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Dario Pisignano

Publications and source records attributed to Dario Pisignano.

71 records · Page 4Linked to original sources

Cooperativity in the enhanced piezoelectric response of polymer nanowires

We provide a detailed insight into piezoelectric energy generation from arrays of polymer nanofibers. For sake of comparison, we firstly measure individual poly(vinylidenefluoride-co-trifluoroethylene) (P(VDF-TrFe)) fibers at well-defined levels of compressive stress. Under an applied load of 2 mN, single nanostructures generate a voltage of 0.45 mV. We show that under the same load conditions, fibers in dense arrays exhibit a voltage output higher by about two orders of magnitude. Numerical modelling studies demonstrate that the enhancement of the piezoelectric response is a general phenomenon associated to the electromechanical interaction among adjacent fibers, namely a cooperative effect depending on specific geometrical parameters. This establishes new design rules for next piezoelectric nano-generators and sensors.

cond-mat.mtrl-sci↗

Ultrathin fibres from electrospinning experiments under driven fast-oscillating perturbations

The effects of a driven fast-oscillating spinneret on the bending instability of electrified jets, leading to the formation of spiral structures in electrospinning experiments with charged polymers, are explored by means of extensive computer simulations. It is found that the morphology of the spirals can be placed in direct correspondence with the oscillation frequency and amplitude. In particular, by increasing the oscillation amplitude and frequency, thinner fibres can be extracted by the same polymer material, thereby opening design scenarios in electrospinning experiments.

physics.flu-dyn↗

Physically transient photonics: random vs. distributed feedback lasing based on nanoimprinted DNA

The authors report on a room-temperature nanoimprinted, DNA-based distributed feedback (DFB) laser operating at 605 nm. The laser is made of a pure DNA host matrix doped with gain dyes. At high excitation densities, the emission of the untextured dye-doped DNA films is characterized by a broad emission peak with an overall linewidth of 12 nm and superimposed narrow peaks, characteristic of random lasing. Moreover, direct patterning of the DNA films is demonstrated with a resolution down to 100 nm, enabling the realization of both surface-emitting and edge-emitting DFB lasers with a typical linewidth<0.3 nm. The resulting emission is polarized, with a ratio between the TE- and TM-polarized intensities exceeding 30. In addition, the nanopatterned devices dissolve in water within less than two minutes. These results demonstrate the possibility of realizing various physically transient nanophotonics and laser architectures, including random lasing and nanoimprinted devices, based on natural biopolymers.

cond-mat.mtrl-sci↗

Organic nanofibers embedding stimuli-responsive threaded molecular components

While most of the studies on molecular machines have been performed in solution, interfacing these supramolecular systems with solid-state nanostructures and materials is very important in view of their utilization in sensing components working by chemical and photonic actuation. Host polymeric materials, and particularly polymer nanofibers, enable the manipulation of the functional molecules constituting molecular machines, and provide a way to induce and control the supramolecular organization. Here, we present electrospun nanocomposites embedding a self-assembling rotaxane-type system that is responsive to both optical (UV-visible light) and chemical (acid/base) stimuli. The system includes a molecular axle comprised of a dibenzylammonium recognition site and two azobenzene end groups, and a dibenzo[24]crown-8 molecular ring. The dethreading and rethreading of the molecular components in nanofibers induced by exposure to base and acid vapors, as well as the photoisomerization of the azobenzene end groups, occur in a similar manner to what observed in solution. Importantly, however, the nanoscale mechanical function following external chemical stimuli induces a measurable variation of the macroscopic mechanical properties of nanofibers aligned in arrays, whose Young's modulus is significantly enhanced upon dethreading of the axles from the rings. These composite nanosystems show therefore great potential for application in chemical sensors, photonic actuators and environmentally responsive materials.

cond-mat.mtrl-sci↗

A multiscale-multiphysics strategy for numerical modeling of thin piezoelectric sheets

Flexible piezoelectric devices made of polymeric materials are widely used for micro- and nano-electro-mechanical systems. In particular, numerous recent applications concern energy harvesting. Due to the importance of computational modeling to understand the influence that microscale geometry and constitutive variables exert on the macroscopic behavior, a numerical approach is developed here for multiscale and multiphysics modeling of piezoelectric materials made of aligned arrays of polymeric nanofibers. At the microscale, the representative volume element consists in piezoelectric polymeric nanofibers, assumed to feature a linear piezoelastic constitutive behavior and subjected to electromechanical contact constraints using the penalty method. To avoid the drawbacks associated with the non-smooth discretization of the master surface, a contact smoothing approach based on Bézier patches is extended to the multiphysics framework providing an improved continuity of the parameterization. The contact element contributions to the virtual work equations are included through suitable electric, mechanical and coupling potentials. From the solution of the micro-scale boundary value problem, a suitable scale transition procedure leads to the formulation of a macroscopic thin piezoelectric shell element.

physics.comp-ph↗

Random lasing in an organic light-emitting crystal and its interplay with vertical cavity feedback

The simultaneous vertical-cavity and random lasing emission properties of a blue-emitting molecular crystal are investigated. The 1,1,4,4-tetraphenyl-1,3-butadiene samples, grown by physical vapour transport, feature room-temperature stimulated emission peaked at about 430 nm. Fabry-Pérot and random resonances are primed by the interfaces of the crystal with external media and by defect scatterers, respectively. The analysis of the resulting lasing spectra evidences the existence of narrow peaks due to both the built-in vertical Fabry-Pérot cavity and random lasing in a novel, surface-emitting configuration and threshold around 500 microJ cm^-2. The anti-correlation between different modes is also highlighted, due to competition for gain. Molecular crystals with optical gain candidate as promising photonic media inherently supporting multiple lasing mechanisms.

cond-mat.mtrl-sci↗

Effects of non-linear rheology on the electrospinning process: a model study

We develop an analytical bead-spring model to investigate the role of non-linear rheology on the dynamics of electrified jets in the early stage of the electrospinning process. Qualitative arguments, parameter studies as well as numerical simulations, show that the elongation of the charged jet filament is significantly reduced in the presence of a non-zero yield stress. This may have beneficial implications for the optimal design of future electrospinning experiments.

physics.flu-dyn↗

The conformational evolution of elongated polymer solutions tailors the polarization of light-emission from organic nanofibers

Polymer fibers are currently exploited in tremendously important technologies. Their innovative properties are mainly determined by the behavior of the polymer macromolecules under the elongation induced by external mechanical or electrostatic forces, characterizing the fiber drawing process. Although enhanced physical properties were observed in polymer fibers produced under strong stretching conditions, studies of the process-induced nanoscale organization of the polymer molecules are not available, and most of fiber properties are still obtained on an empirical basis. Here we reveal the orientational properties of semiflexible polymers in electrospun nanofibers, which allow the polarization properties of active fibers to be finely controlled. Modeling and simulations of the conformational evolution of the polymer chains during electrostatic elongation of semidilute solutions demonstrate that the molecules stretch almost fully within less than 1 mm from jet start, increasing polymer axial orientation at the jet center. The nanoscale mapping of the local dichroism of individual fibers by polarized near-field optical microscopy unveils for the first time the presence of an internal spatial variation of the molecular order, namely the presence of a core with axially aligned molecules and a sheath with almost radially oriented molecules. These results allow important and specific fiber properties to be manipulated and tailored, as here demonstrated for the polarization of emitted light.

cond-mat.mtrl-sci↗

Polymer nanofibers as novel light-emitting sources and lasing material

Polymer micro- and nano-fibers, made of organic light-emitting materials with optical gain, show interesting lasing properties. Fibers with diameters from few tens of nm to few microns can be fabricated by electrospinning, a method based on electrostatic fields applied to a polymer solution. The morphology and emission properties of these fibers, composed of optically inert polymers embedding laser dyes, are characterized by scanning electron and fluorescence microscopy, and lasing is observed under optical pumping for fluences of the order of 10^2 microJ cm^-2. In addition, light-emitting fibers can be electrospun by conjugated polymers, their blends, and other active organics, and can be exploited in a range of photonic and electronic devices. In particular, waveguiding of light is observed and characterized, showing optical loss coefficient in the range of 10^2-10^3 cm^-1. The reduced size of these novel laser systems, combined with the possibility of achieving wavelength tunability through transistor or other electrode-based architectures embedding non-linear molecular layers, and with their peculiar mechanical robustness, open interesting perspectives for realizing miniaturized laser sources to integrate on-chip optical sensors and photonic circuits.

cond-mat.mtrl-sci↗

Local mechanical properties of electrospun fibers correlate to their internal nanostructure

The properties of polymeric nanofibers can be tailored and enhanced by properly managing the structure of the polymeric molecules at the nanoscale. Although electrospun polymer fibers are increasingly exploited in many technological applications, their internal nanostructure, determining their improved physical properties, is still poorly investigated and understood. Here, we unravel the internal structure of electrospun functional nanofibers made by prototype conjugated polymers. The unique features of near field optical measurements are exploited to investigate the nanoscale spatial variation of the polymer density, evidencing the presence of a dense internal core embedded in a less dense polymeric shell. Interestingly, nanoscale mapping the fiber Young's modulus demonstrates that the dense core is stiffer than the polymeric, less dense shell. These findings are rationalized by developing a theoretical modeling and simulations of the polymer molecular structural evolution during the electrospinning process. This model predicts that the stretching of the polymer network induces a contraction towards the jet center of the network with a local increase of the polymer density, as observed in the solid structure. The found complex internal structure opens interesting perspective for improving and tailoring the molecular morphology and multifunctional electronic and optical properties of polymer fibers.

cond-mat.mtrl-sci↗

Near-field electrospinning of conjugated polymer light-emitting nanofibers

The authors report on the realization of ordered arrays of light-emitting conjugated polymer nanofibers by near-field electrospinning. The fibers, made by poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene], have diameters of few hundreds of nanometers and emission peaked at 560 nm. The observed blue-shift compared to the emission from reference films is attributed to different polymer packing in the nanostructures. Optical confinement in the fibers is also analyzed through self-waveguided emission. These results open interesting perspectives for realizing complex and ordered architectures by light-emitting nanofibers, such as photonic circuits, and for the precise positioning and integration of conjugated polymer fibers into light-emitting devices.

cond-mat.mtrl-sci↗

High Performance Piezoelectric Devices Based on Aligned Arrays of Nanofibers of Poly[(vinylidenefluoride-co-trifluoroethylene]

Multifunctional capability, flexible design, rugged lightweight construction, and self-powered operation are desired attributes for electronics that directly interface with the human body or with advanced robotic systems. For these and related applications, piezoelectric materials, in forms that offer the ability to bend and stretch, are attractive for pressure/force sensors and mechanical energy harvesters. In this paper we introduce a large area, flexible piezoelectric material that consists of sheets of electrospun fibers of the polymer poly[(vinylidenefluoride-co-trifluoroethylene]. The flow and mechanical conditions associated with the spinning process yield free-standing, three-dimensional architectures of aligned arrangements of such fibers, in which the polymer chains adopt strongly preferential orientations. The resulting material offers exceptional piezoelectric characteristics, to enable, as an example, ultra-high sensitivity for measuring pressure, even at exceptionally small values (0.1 Pa). Quantitative analysis provides detailed insights into the pressure sensing mechanisms, and engineering design rules. Applications range from self-powered micro-mechanical elements, to self-balancing robots and sensitive impact detectors.

cond-mat.mtrl-sci↗

Bright light emission and waveguiding in conjugated polymer nanofibers electrospun from organic-salt added solutions

Light emitting electrospun nanofibers of poly-[(9,9-dioctylfluorenyl-2,7-diyl)-co-(N,N'-diphenyl)-N,N'-di(p-butyl-oxy-phenyl)-1,4-diaminobenzene)] (PFO-PBAB) are produced by electrospinning under different experimental conditions. In particular, uniform fibers with average diameter of 180 nm are obtained by adding an organic salt to the electrospinning solution. The spectroscopic investigation assesses that the presence of the organic salt does not alter the optical properties of the active material, therefore providing an alternative approach for the fabrication of highly emissive conjugated polymer nanofibers. The produced nanofibers display self-waveguiding of light, and polarized photoluminescence, which is especially promising for embedding active electrospun fibers in sensing and nanophotonic devices.

cond-mat.mtrl-sci↗

Polarized superradiance from delocalized exciton transitions in tetracene single crystals

Polarized superradiant emission and exciton delocalization in tetracene single crystals are reported. Polarization-, time-, and temperature-resolved spectroscopy evidence the complete polarization of the zero-phonon line of the intrinsic tetracene emission from both the lower (F state) and the upper (thermally activated) Davydov excitons. The superradiance of the F emission is substantiated by a nearly linear decrease of the radiative lifetime with temperature, being fifteen times shorter at 30 K compared to the isolated molecule, with an exciton delocalization of about 40 molecules.

cond-mat.mtrl-sci↗

Effect of finite terms on the truncation error of Mie series

The finite sum of the squares of the Mie coefficients is very useful for addressing problems of classical light scattering. An approximate formula available in the literature, and still in use today, has been developed to determine a priori the number of the most significant terms needed to evaluate the scattering cross section. Here we obtain an improved formula, which includes the number of terms needed for determining the scattering cross section within a prescribed relative error. This is accomplished using extended precision computation, for a wide range of commonly used size parameters and indexes of refraction. The revised formula for the finite number of terms can be a promising and valuable approach for efficient modeling light scattering phenomena.

physics.optics↗

Rotational dynamics of optically trapped polymeric nanofibers

The optical trapping of polymeric nanofibers and the characterization of the rotational dynamics are reported. A strategy to apply a torque to a polymer nanofiber, by tilting the trapped fibers using a symmetrical linear polarized Gaussian beam is demonstrated. Rotation frequencies up to 10 Hz are measured, depending on the trapping power, the fiber length and the tilt angle. A comparison of the experimental rotation frequencies in the different trapping configurations with calculations based on optical trapping and rotation of linear nanostructures through a T-Matrix formalism, accurately reproduce the measured data, providing a comprehensive description of the trapping and rotation dynamics.

physics.optics↗