Emanuela Piscopiello

Light-emitting nanocomposite CdS–polymer electrospun fibres via in situ nanoparticle generation

We report on the simple, in situ generation of CdS nanocrystals inside electrospun polymer fibres by thermal decomposition of a cadmium thiolate precursor, leading to nanocomposite light-emitting fibres. The modifications induced in the precursor by the thermal decomposition are investigated by a morphological, structural and spectroscopic analysis of the resulting nanocomposite fibres. This approach allows us to overcome nanofabrication difficulties related to disfavoured micro- or nanofluidic molecular flow as given by the direct incorporation of particles in the electrospinning solution. This method therefore enables the synthesis of luminescent, CdS-based composite fibres with emission peaked in the visible range, suitable as building blocks for nanophotonic devices based on light-emitting nanomaterials.

Hydrogen sorption in Pd-decorated Mg―MgO core-shell nanoparticles

Mg nanoparticles with metal-oxide core-shell morphology were synthesized by inert-gas condensation and decorated by in situ Pd deposition. Transmission electron microscopy and x-ray diffraction underline the formation of a noncontinuous layer with Pd clusters on top of the MgO shell. Even in the presence of a thick MgO interlayer, a modest (2 at. %) Pd decoration deeply enhances the hydrogen sorption properties: previously inert nanoparticles exhibit metal-hydride transformation with fast kinetics and gravimetric capacity above 5 wt %.

CdS-polymer nanocomposites and light-emitting fibers by in situ electron-beam synthesis and lithography.

A straightforward, electron-beam induced synthesis and patterning approach to the in situ generation of CdS nanocrystals in nanocomposite films and light-emitting electrospun nanofibers is used. Smartly combining room-temperature nanoimprinting, electrospinning, and electron-beam decomposition of nanocrystal precursors and subsequent nucleation of nanoparticles in a polymer matrix allows exploitation of the most favorable flow conditions of organics to produce various nanocomposite nanostructures.

Metal-hydride transformation kinetics in Mg nanoparticles

The hydrogen sorption kinetics of magnesium nanoparticles prepared by inert gas condensation and coated by a magnesium oxide layer were investigated by a volumetric apparatus. The metal-hydride transformation was studied by transmission electron microscopy of the nanoparticles both in the as-prepared state and after hydrogen cycling. In small nanoparticles (≈35 nm) hydride formation proceeds by one-dimensional growth controlled by diffusion through the hydride, while the reverse transformation to metal involves interface-controlled three-dimensional growth of nuclei formed at constant rate. Large nanoparticles (≈450 nm) exhibit very low reactivity attributed to reduced probability of hydrogen dissociation/recombination and nucleation at the particle surface.

Mono- and bi-functional arenethiols as surfactants for gold nanoparticles: synthesis and characterization.

Stable gold nanoparticles stabilized by different mono and bi-functional arenethiols, namely, benzylthiol and 1,4-benzenedimethanethiol, have been prepared by using a modified Brusts two-phase synthesis. The size, shape, and crystalline structure of the gold nanoparticles have been determined by high-resolution electron microscopy and full-pattern X-ray powder diffraction analyses. Nanocrystals diameters have been tuned in the range 2 ÷ 9 nm by a proper variation of Au/S molar ratio. The chemical composition of gold nanoparticles and their interaction with thiols have been investigated by X-ray photoelectron spectroscopy. In particular, the formation of networks has been observed with interconnected gold nanoparticles containing 1,4-benzenedimethanethiol as ligand.

Synthesis and Microstructural Investigations of Organometallic Pd(II) Thiol-Gold Nanoparticles Hybrids

In this work the synthesis and characterization of gold nanoparticles functionalized by a novel thiol-organometallic complex containing Pd(II) centers is presented. Pd(II) thiol,trans, trans-[dithiolate-dibis(tributylphosphine)dipalladium(II)-4,4′-diethynylbiphenyl] was synthesized and linked to Au nanoparticles by the chemical reduction of a metal salt precursor. The new hybrid made of organometallic Pd(II) thiol-gold nanoparticles, shows through a single S bridge a direct link between Pd(II) and Au nanoparticles. The size-control of the Au nanoparticles (diameter range 2–10 nm) was achieved by choosing the suitable AuCl4−/thiol molar ratio. The size, strain, shape, and crystalline structure of these functionalized nanoparticles were determined by a full-pattern X-ray powder diffraction analysis, high-resolution TEM, and X-ray photoelectron spectroscopy. Photoluminescence spectroscopy measurements of the hybrid system show emission peaks at 418 and 440 nm. The hybrid was exposed to gaseous NOxwith the aim to evaluate the suitability for applications in sensor devices; XPS measurements permitted to ascertain and investigate the hybrid –gas interaction.

Physical properties evolution of sputtered zirconium oxynitride films: effects of the growth temperature

Zirconium oxynitride (ZrNO) films were deposited by RF reactive magnetron sputtering in water vapour–nitrogen atmosphere varying the deposition temperature from RT to 600 °C. Optical analysis, x-ray diffraction, x-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) are the employed characterization techniques to investigate the influence of the substrate temperature on the films physical properties. It was found that the variation of the substrate temperature from RT to 600 °C caused a structural transition from cubic phase of Zr2ON2 to ZrN one, as confirmed by TEM observations too. In particular, Forouhi–Bloomer dispersion equations for optical parameters (n and k) and deconvolution of XPS spectra allowed further chemical properties be elucidated. They also permitted identification of two oxynitride phases, γ phase (Eg = 1.94 eV) and β phase (Eg = 1.7 eV), and an over-stoichiometric nitride one. The use of [Ec − Ev] values helped to confirm further the distinction between (γ, β)-phases and N-rich zirconium nitride compound, which is unachievable by using only Eg values.

Exchange bias and interface structure in the Ni/NiO nanogranular system

The exchange bias (EB) effect has been studied in Ni/NiO nanogranular samples obtained by annealing in H2, at different temperatures (200 ? Tann ? 300??C), NiO powder previously ball-milled for 20?h. Typically, the samples consist of Ni nanoparticles (mean size of 10?18?nm) embedded in a nanocrystalline NiO matrix. With increasing Tann, the Ni fraction varies from 4% up to 69%. The exchange field depends on the Ni amount, being maximum (~600?Oe), at T = 5?K, in the sample with 15% Ni. In all the samples, the EB effect vanishes at T = 200?K. The structural features of the samples have been investigated by x-ray diffraction, electron microscopy and extended x-ray absorption fine structure and the low-temperature magneto-thermal behaviour has been thoroughly analyzed. The results show the existence of a structurally and magnetically disordered NiO component, which plays the key role in the EB mechanism.

Photon-induced formation of CdS nanocrystals in selected areas of polymer matrices

We demonstrate light-induced formation of semiconductor quantum dots in TOPAS® polymer matrix with very high control of their size and their spatial localization. Irradiation with UV laser pulses of polymer films embedding Cd thiolate precursors results in the formation of cadmium sulfide nanocrystals well confined in the irradiation area, through a macroscopically nondestructive procedure for the host matrix. With increasing number of laser pulses, we accomplish the formation of nanoparticles with gradually increasing dimensions, resulting in the dynamic change of the spectra emitted by the formed nanocomposite areas. The findings are supported by x-ray diffraction and transmission electron microscopy measurements.

Tryptophan-functionalized gold nanoparticles for deep UV imaging of microbial cells

Biocompatible fluorescent nanostructures were prepared by a functionalization of gold nanoparticles with the amino acid tryptophan. The gold-tryptophan bioconjugates were investigated by TEM and HRTEM and various spectroscopy methods (XPS, FTIR, UV-vis and photoluminescence). It was found that the gold nanoparticles, initially 8 nm in diameter, aggregate in the presence of the amino acid. From the XPS and FTIR spectroscopy results, it was concluded that the tryptophan gold interactions mainly take place via indole and carboxyl groups. Although the indole group is involved in the interaction with the gold surfaces, the tryptophan-gold hybrids showed strong fluorescence due to the presence of multilayers of tryptophan. Deep ultra violet (DUV) imaging performed at the SOLEIL synchrotron showed that it is possible to detect these hybrid nanostructures within Escherichia coli cells.