Vito Fasano

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.

Near-field electrospinning of light-emitting conjugated polymer nanofibers

Ordered arrays of light-emitting conjugated polymer nanofibers are realized by near-field electrospinning.

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–vis 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.

Distributed Feedback Imprinted Electrospun Fiber Lasers

Imprinted, distributed feedback lasers are demonstrated on individual, active electrospun polymer nanofibers. In addition to advantages related to miniaturization, optical confinement and grating nanopatterning lead to a significant threshold reduction compared to conventional thin-film lasers. The possibility of imprinting arbitrary photonic crystal geometries on electrospun lasing nanofibers opens new opportunities for realizing optical circuits and chips.

Y thin films grown by pulsed laser ablation

The effects of laser fluence on the growth characteristics and surface morphology of yttrium films grown by pulsed laser deposition are investigated. The presence of droplets in the deposited films, which is the main drawback of pulsed laser deposition technique, was studied at different laser fluences. The morphology and the structure of the grown films were studied by scanning-electron microscopy and x-ray diffraction, respectively. Careful scanning-electron microscope investigations obtained by tilting the samples show that the droplets arrive to the substrate in the molten phase. The ablation rate measured at five different laser fluences (0.9–7.6 J/cm2) shows a nonlinear trend correlated with the presence of the plasma-shielding effect. The present interest in the deposition of yttrium thin films by laser ablation is due to the well-known photoemission characteristics of this metal. Depositing good-quality thin films with high adhension and low droplet density will improve the performance of photocat...

Controlled Atmosphere Electrospinning of Organic Nanofibers with Improved Light Emission and Waveguiding Properties

Electrospinning in controlled nitrogen atmosphere is developed for the realization of active polymer nanofibers. Fibers electrospun under controlled atmospheric conditions are found to be smoother and more uniform than samples realized by conventional electrospinning processes performed in air. In addition, they exhibit peculiar composition, incorporating a greatly reduced oxygen content during manufacturing, which favors enhanced optical properties and increases emission quantum yield. Active waveguides with optical losses coefficients lowered by 10 times with respect to fibers spun in air are demonstrated through this method. These findings make the process very promising for the highly controlled production of active polymer nanostructures for photonics, electronics and sensing.

Anisotropic Conjugated Polymer Chain Conformation Tailors the Energy Migration in Nanofibers

Conjugated polymers are complex multichromophore systems, with emission properties strongly dependent on the electronic energy transfer through active subunits. Although the packing of the conjugated chains in the solid state is known to be a key factor to tailor the electronic energy transfer and the resulting optical properties, most of the current solution-based processing methods do not allow for effectively controlling the molecular order, thus making the full unveiling of energy transfer mechanisms very complex. Here we report on conjugated polymer fibers with tailored internal molecular order, leading to a significant enhancement of the emission quantum yield. Steady state and femtosecond time-resolved polarized spectroscopies evidence that excitation is directed toward those chromophores oriented along the fiber axis, on a typical time scale of picoseconds. These aligned and more extended chromophores, resulting from the high stretching rate and electric field applied during the fiber spinning process, lead to improved emission properties. Conjugated polymer fibers are relevant to develop optoelectronic plastic devices with enhanced and anisotropic properties.

Rolling particle lithography by soft polymer microparticles

Elastomeric polymeric microspheres are employed as a direct-writing tool for the continuous delivery of molecular materials. The mechanical properties enabling patterning are investigated and modelled. The proposed approach provides a low cost and versatile lithographic method for transferring features with real-time dynamic control.

Biomineral Amorphous Lasers through Light‐Scattering Surfaces Assembled by Electrospun Fiber Templates

New materials aim at exploiting the great control of living organisms over molecular architectures and minerals. Optical biomimetics has been widely developed by microengineering, leading to photonic components with order resembling those found in plants and animals. These systems, however, are realized by complicated and adverse processes. Here we show how biomineralization might enable the one-step generation of components for amorphous photonics, in which light is made to travel through disordered scattering systems, and particularly of active devices such as random lasers, by using electrospun fiber templates. The amount of bio-enzymatically produced silica is related to light-scattering capacity and the resulting organosilica surfaces exhibit a transport mean free path for light as low as 3 micron, and lasing with linewidth below 0.2 nm. The resulting, complex optical material is characterized and modelled to elucidate scattered fields and lasing performance. Tightly-controlled nanofabrication of direct biological inspiration establishes a new concept for the additive manufacturing of engineered light-diffusing materials and photonic components, not addressed by existing technologies.

Electrospun conjugated polymer nanofibers as miniaturized light sources: control of morphology, optical properties, and assembly

Light-emitting nanostructures made by conjugated polymers show interesting emission and electronic properties. In this work we report on novel approaches for the fabrication and control of light-emitting nanofibers by electrospinning. The shape, size and light-emitting properties of the fibers can be specifically tailored by acting on the composition of the solution used for the electrospinning process, an approach allowing for obtaining fibers ranging from micrometer-sized ribbons to almost cylindrical fibers with diameters down to few hundreds of nanometers. Moreover, following proper process optimization these fibers can also be precisely positioned in ordered arrays by near-field electrospinning, a method that exploits the stable region of the polymer jet. The possibility of precisely shaping the conjugated polymer fibers and of assembling the fiber in ordered arrays, combined with enhanced emission properties, opens interesting perspectives for developing novel emitting flexible nanomaterials suitable for light sourcing and optical sensing.