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Combined dry-wet transient materials and devices are introduced, which are based on water-dissolvable dye-doped polymers layered onto non-polar cyclic hydrocarbon sublimating substrates. Light-emitting heterostructures showing amplified spontaneous emission are used as illumination sources for speckle-free, full-field imaging, and transient optical labels are realized that incorporate QR codes with stably encoded information. The transient behavior is also studied at the microscopic scale, highlighting the real time evolution of material domains in the sublimating compound. Finally, the exhausted components are fully soluble in water thus being naturally degradable., Comment: 30 pages, 15 figures

Lasers based on biological materials are attracting an increasing interest in view of their use in integrated and transient photonics. DNA as optical biopolymer in combination with highly-emissive dyes has been reported to have excellent potential in this respect, however achieving miniaturized lasing systems based on solid-state DNA shaped in different geometries to confine and enhance emission is still a challenge, and physico-chemical mechanisms originating fluorescence enhancement are not fully understood. Herein, a class of wavelength-tunable lasers based on DNA nanofibers is demonstrated, for which optical properties are highly controlled through the system morphology. A synergistic effect is highlighted at the basis of lasing action. Through a quantum chemical investigation, we show that the interaction of DNA with the encapsulated dye leads to hindered twisting and suppressed channels for the non-radiative decay. This is combined with effective waveguiding, optical gain, and tailored mode confinement to promote morphologically-controlled lasing in DNA-based nanofibers. The results establish design rules for the development of bright and tunable nanolasers and optical networks based on DNA nanostructures., Comment: 31 pages, 11 figures and 2 tables

The miniaturization of diagnostic devices that exploit optical detection schemes requires the design of light-sources combining small size, high performance for effective excitation of chromophores, and mechanical flexibility for easy coupling to components with complex and non-planar shapes. Here, ZnO nanowire-in-fiber hybrids with internal architectural order are introduced, exhibiting a combination of polarized stimulated emission, low propagation losses of light modes, and structural flexibility. Ultrafast transient absorption experiments on the electrospun material show optical gain which gives rise to amplified spontaneous emission, with threshold lower than the value found in films. These systems are highly flexible and can conveniently conform to curved surfaces, which makes them appealing active elements for various device platforms, such as bendable lasers, optical networks and sensors, as well as for application in bioimaging, photo-crosslinking, and optogenetics., Comment: 50 pages, 17 figures, 1 table, ACS Nano, 2020

Molybdenum disulfide (MoS2) has been attracting extraordinary attention for its intriguing optical, electronic and mechanical properties. Here we demonstrate hybrid, organic-inorganic light-emitting nanofibers based on MoS2 nanoparticle dopants obtained through a simple and inexpensive sonication process in N-methyl-2-pyrrolidone and successfully encapsulated in polymer filaments. Defectiveness is found to be kept low, and stoichiometry preserved, by the implemented, gentle exfoliation method that allows the MoS2 nanoparticles to be produced. So-achieved hybrid fibers are smooth, uniform, flawless, and exhibit bright and continuous light emission. Moreover, they show significant capability of waveguiding self-emitted light along their longitudinal axis. These findings suggest the use of emissive MoS2 fibers enabled by gentle exfoliation methods as novel and highly promising optical material for building sensing surfaces and as components of photonic circuits., Comment: 22 pages, 9 figures, Nanoscale, 2018

Hybrid conjugated polymer/fullerene filaments based on MEH-PPV/PVP/PCBM are prepared by electrospinning, and their properties assessed by scanning electron, atomic and lateral force, tunnelling, and confocal microscopy, as well as by attenuated total reflection Fourier transform-infrared spectroscopy, photoluminescence quantum yield and spatially-resolved fluorescence. Highlighted features include ribbon-shape of the realized fibers, and the persistence of a network serving as a template for heterogeneous active layers in solar cell devices. A set of favorable characteristics is evidenced in this way in terms of homogeneous charge transport behavior and formation of effective interfaces for diffusion and dissociation of photogenerated excitons. The interaction of the organic filaments with light, exhibiting specific light-scattering properties of the nanofibrous mat, might also contribute to spreading incident radiation across the active layers, thus potentially enhancing photovoltaic performance. This method might be applied to other electron donor-electron acceptor material systems for the fabrication of solar cell devices enhanced by nanofibrillar morphologies embedding conjugated polymers and fullerene compounds., Comment: 35 pages, 9 figures

Random lasers are based on disordered materials with optical gain. These devices can exhibit either intensity or resonant feedback, relying on diffusive or interference behaviour of light, respectively, which leads to either coupling or independent operation of lasing modes. We study for the first time these regimes in complex, solid-state nanostructured materials. The number of lasing modes and their intensity correlation features are found to be tailorable in random lasers made of light-emitting, electrospun polymer fibers upon nanoparticle doping. By material engineering, directional waveguiding along the length of fibers is found to be relevant to enhance mode correlation in both intensity feedback and resonant feedback random lasing. The here reported findings can be used to establish new design rules for tuning the emission of nano-lasers and correlation properties by means of the compositional and morphological properties of complex nanostructured materials., Comment: 30 pages, 10 figures

Electromechanical coupling through piezoelectric polymer chains allows the emission of organic molecules in active nanowires to be tuned. This effect is evidenced by highly bendable arrays of counter-ion dye-doped nanowires made of a poly(vinylidenefluoride) copolymer. A reversible redshift of the dye emission is found upon the application of dynamic stress during highly accurate bending experiments. By density functional theory calculations it is found that these photophysical properties are associated with mechanical stresses applied to electrostatically interacting molecular systems, namely to counterion-mediated states that involve light-emitting molecules as well as charged regions of piezoelectric polymer chains. These systems are an electrostatic class of supramolecular functional stress-sensitive units, which might impart new functionalities in hybrid molecular nanosystems and anisotropic nanostructures for sensing devices and soft robotics., Comment: 32 pages, 18 figures

The intrinsic flexible character of polymeric materials also causes remarkable strain deformations along directions perpendicular to the applied stress. Here the biaxial response in the shear piezoelectricity of polyvinylidenefluoride copolymers is analyzed and their full piezoelectric tensors are provided. The microscopic shear is exploited in single suspended nanowires bent by localized loading to couple flexural deformation and transverse piezoelectric response., Comment: 36 pages, 10 figures, 2 tables, 49 references, Advanced Materials, 2016

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 ten 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., Comment: 26 pages, 11 figures

The use of UV light sources is highly relevant in many fields of science, being directly related to all those detection and diagnosis procedures which are based on fluorescence spectroscopy. Depending on the specific application, UV light-emitting materials are desired to feature a number of opto-mechanical properties, including brightness, optical gain for being used in laser devices, flexibility to conform with different lab-on-chip architectures, and tailorable wettability to control and minimize their interaction with ambient humidity and fluids. In this work, we introduce multifunctional, UV-emitting electrospun fibers with both optical gain and anisotropic hydrophobicity greatly enhanced compared to films. Fibers are described by the onset of a composite wetting state and their arrangement in uniaxial arrays further favours liquid directional control. The low gain threshold and optical losses, the plastic nature and the flexibility and stability of these UV-emitting fibers make them interesting for building light-emitting devices and microlasers. Furthermore, the found anisotropic hydrophobicity is strongly synergic with optical properties, reducing interfacial interactions with liquids and enabling smart functional surfaces for droplet microfluidic and wearable applications., Comment: 25 pages, 11 figures

In metal-enhanced fluorescence (MEF), the localized surface plasmon resonances of metallic nanostructures amplify the absorption of excitation light and assist in radiating the consequent fluorescence of nearby molecules to the far-field. This effect is at the base of various technologies that have strong impact on fields such as optics, medical diagnostics and biotechnology. Among possible emission bands, those in the near-infrared (NIR) are particularly intriguing and widely used in proteomics and genomics due to its noninvasive character for biomolecules, living cells, and tissues, which greatly motivates the development of effective, and eventually multifunctional NIR-MEF platforms. Here we demonstrate NIR-MEF substrates based on Au nanocages micropatterned with a tight spatial control. The dependence of the fluorescence enhancement on the distance between the nanocage and the radiating dipoles is investigated experimentally and modeled by taking into account the local electric field enhancement and the modified radiation and absorption rates of the emitting molecules. At a distance around 80 nm, a maximum enhancement up to 2-7 times with respect to the emission from pristine dyes (in the region 660 nm-740 nm) is estimated for films and electrospun nanofibers. Due to their chemical stability, finely tunable plasmon resonances, and large light absorption cross sections, Au nanocages are ideal NIR-MEF agents. When these properties are integrated with the hollow interior and controllable surface porosity, it is feasible to develop a nanoscale system for targeted drug delivery with the diagnostic information encoded in the fluorophore., Comment: 41 pages, 18 figures

Electrospun polymer jets are imaged for the first time at an ultra-high rate of 10,000 frames per second, investigating the process dynamics, and the instability propagation velocity and displacement in space. The polymer concentration, applied voltage bias and needle-collector distance are systematically varied, and their influence on the instability propagation velocity and on the jet angular fluctuations analyzed. This allows us to unveil the instability formation and cycling behavior, and its exponential growth at the onset, exhibiting radial growth rates of the order of 10^3 s^-1. Allowing the conformation and evolution of polymeric solutions to be studied in depth, high-speed imaging at sub-ms scale shows a significant potential for improving the fundamental knowledge of electrified jets, leading to obtain finely controllable bending and solution stretching in electrospinning, and consequently better designed nanofibers morphologies and structures., Comment: 23 pages, 9 figures

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., Comment: 31 pages, 11 figures, 1 table

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., Comment: 20 pages, 5 figures, 31 references

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 B\'ezier 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., Comment: 11 pages, 6 pages, 21 references

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 thin piezoelectric sheets made of aligned arrays of polymeric nanofibers, manufactured by electrospinning. At the microscale, the representative volume element consists in piezoelectric polymeric nanofibers, assumed to feature a piezoelastic behavior and subjected to electromechanical contact constraints. The latter are incorporated into the virtual work equations by formulating suitable electric, mechanical and coupling potentials and the constraints are enforced by using the penalty method. From the solution of the micro-scale boundary value problem, a suitable scale transition procedure leads to identifying the performance of a macroscopic thin piezoelectric shell element., Comment: 22 pages, 13 figures

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., Comment: 7 pages, 3 figures, 27 references. Invited contribution. Copyright (2013) Society of Photo Optical Instrumentation Engineers. One print or electronic copy may be made for personal use only. Systematic reproduction and distribution, duplication of any material in this paper for a fee or for commercial purposes, or modification of the content of the paper are prohibited

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., Comment: 49 pages, 16 figures

Nanomaterials made of active fibers have the potential to become new functional components of light-emitting sources in the visible and near-IR range, lasers, and electronic devices, Comment: 7 pages, 2 figures, 17 references. Invited contribution. Copyright (2013) Society of Photo Optical Instrumentation Engineers. One print or electronic copy may be made for personal use only. Systematic reproduction and distribution, duplication of any material in this paper for a fee or for commercial purposes, or modification of the content of the paper are prohibited Spie Newsroom, 26 August 2013