Vincenzo Grillo

Nonhydrolytic Synthesis of High-Quality Anisotropically Shaped Brookite TiO2 Nanocrystals

A surfactant-assisted nonaqueous strategy, relying on high-temperature aminolysis of titanium carboxylate complexes, has been developed to access anisotropically shaped TiO2 nanocrystals selectively trapped in the metastable brookite phase. Judicious temporal manipulation of precursor supply to the reaction mixture enables systematic tuning of the nanostructure geometric features over an exceptionally wide dimensional range (30-200 nm). Such degree of control is rationalized within the frame of a self-regulated phase-changing seed-catalyzed mechanism, in which homogeneous nucleation, on one side, and heterogeneous nucleation/growth processes, on the other side, are properly balanced while switching from the anatase to the brookite structures, respectively, in a continuous unidirectional crystal development regime. The time variation of the chemical potential for the monomer species in the solution, the size dependence of thermodynamic structural stability of the involved titania polymorphs, and the reduced activation barrier for brookite nucleation onto initially formed anatase seeds play decisive roles in the crystal-phase- and shape-tailored growth of titania nanostructures by the present approach.

Metallic-like Stoichiometric Copper Sulfide Nanocrystals: Phase- and Shape-Selective Synthesis, Near-Infrared Surface Plasmon Resonance Properties, and Their Modeling

In the realm of semiconductor nanomaterials, a crystal lattice heavily doped with cation/anion vacancies or ionized atomic impurities is considered to be a general prerequisite to accommodating excess free carriers that can support localized surface plasmon resonance (LSPR). Here, we demonstrate a surfactant-assisted nonaqueous route to anisotropic copper sulfide nanocrystals, selectively trapped in the covellite phase, which can exhibit intense, size-tunable LSPR at near-infrared wavelengths despite their stoichiometric, undoped structure. Experimental extinction spectra are satisfactorily reproduced by theoretical calculations performed by the discrete dipole approximation method within the framework of the Drude-Sommerfeld model. The LSPR response of the nanocrystals and its geometry dependence are interpreted as arising from the inherent metallic-like character of covellite, allowed by a significant density of lattice-constitutional valence-band free holes. As a consequence of the unique electronic properties of the nanocrystals and of their monodispersity, coherent excitation of symmetric radial breathing modes is observed for the first time in transient absorption experiments at LSPR wavelengths.

Architectural Control of Seeded-Grown Magnetic−Semicondutor Iron Oxide−TiO2 Nanorod Heterostructures: The Role of Seeds in Topology Selection

A colloidal nonaqueous approach to semiconductor-magnetic hybrid nanocrystals (HNCs) with selectable heterodimer topologies and tunable geometric parameters is demonstrated. Brookite TiO(2) nanorods, distinguished by a curved shape-tapered profile with richly faceted terminations, are exploited as substrate seeds onto which a single spherical domain of inverse spinel iron oxide can be epitaxially grown at either one apex or any location along their longitudinal sidewalls in a hot surfactant environment. The topologically controlled arrangement of the component material lattices, the crystallographic relationships holding between them, and strain distribution across individual heterostructures have been studied by combining X-ray diffraction and absorption techniques with high-resolution transmission electron microscopy investigations. Supported by such structural knowledge, the synthetic achievements are interpreted within the frame of various mechanistic models offering complementary views of HNC formation. The different HNC architectures are concluded to be almost equivalent in terms of surface-interface energy balance associated with their formation. HNC topology selection is rationalized on the basis of a diffusion-limited mechanism allowing iron oxide heterogeneous nucleation and growth on the TiO(2) nanorods to switch from a thermodynamically controlled to a kinetically overdriven deposition regime, in which the anisotropic reactivity offered by the uniquely structured seeds is accentuated under high spatially inhomogeneous monomer fluxes. Finally, the multifunctional capabilities of the heterostructures are highlighted through illustration of their magnetic and photocatalytic properties, which have been found to diverge from those otherwise exhibited by their individual material components and physical mixture counterparts.

InAs/InSb nanowire heterostructures grown by chemical beam epitaxy

We report the Au-assisted chemical beam epitaxy growth of defect-free zincblende InSb nanowires. The grown InSb segments are the upper sections of InAs/InSb heterostructures on InAs(111)B substrates. We show, through HRTEM analysis, that zincblende InSb can be grown without any crystal defects such as stacking faults or twinning planes. Strain-map analysis demonstrates that the InSb segment is nearly relaxed within a few nanometers from the interface. By post-growth studies we have found that the catalyst particle composition is AuIn(2), and it can be varied to a AuIn alloy by cooling down the samples under TDMASb flux.

Self-catalyzed growth of GaAs nanowires on cleaved Si by molecular beam epitaxy

Self-assembled GaAs nanowires have been grown on Si by molecular beam epitaxy without the use of any outside metal catalyst. The growth occurs on Si facets obtained by the cleavage of Si(100) substrates. The growth has been obtained with or without Ga pre-deposition. In both cases two kinds of nanowires have been obtained. The wires of the first type clearly present a Ga droplet at their free end and have a lattice structure that is wurtzite for wide regions beneath the Ga droplet. The second type, in contrast, ends with pyramidally shaped GaAs and has a crystal lattice that is mainly zincblende with only a few and small wurtzite regions, if any. The Ga-ended nanowires are longer than the others and thinner on average. The experimental findings suggest that the two types of nanowires grow after different growth processes.

Highly efficient electron vortex beams generated by nanofabricated phase holograms

We propose an improved type of holographic-plate suitable for the shaping of electron beams. The plate is fabricated by a focused ion beam on a silicon nitride membrane and introduces a controllable phase shift to the electron wavefunction. We adopted the optimal blazed-profile design for the phase hologram, which results in the generation of highly efficient (25%) electron vortex beams. This approach paves the route towards applications in nano-scale imaging and materials science.

STEM_CELL: A software tool for electron microscopy: Part I—simulations

The software STEM_CELL, here presented, is a useful tool for (S) TEM simulation. In particular innovative solutions are presented in (1) the supercell manipulation and parameters setting (2) simulation execution through the modified Kirkland routines (3) simulation post-processing with extended output and comprehensive graphic tools (4) image contrast interpretation through a strain channeling equation accounting for strain effects in STEM-ADF.

Room temperature luminescent InGaAs/GaAs core-shell nanowires

InGaAs/GaAs core-shell nanowires have been grown by molecular beam epitaxy. The core-shell nanowires show room temperature photoluminescence. At low temperatures their luminescence intensity is two to three orders of magnitudes larger than that of parent InGaAs nanowires grown without external GaAs shell. The nanowires have been structurally characterized by scanning electron microscopy and transmission electron microscopy.

Structure and stability of nickel/nickel oxide core–shell nanoparticles

The results of a combined x-ray photoelectron spectroscopy (XPS) and high resolution transmission electron microscopy (HR-TEM) study of Ni nanoparticles (NP), before and after oxidation, are presented. An experimental set-up was realized for the preparation and study of pre-formed NP films, concentrating the attention on Ni NP in the diameter range between 4 and 8 nm. The XPS data were taken in situ from NPs after different stages of oxidation, including controlled dosing of O(2) gas in the experimental system and exposure to the atmosphere. The Ni 2p structure is a combination of spectra from metallic Ni in the NP core and from the oxide shell. The signal from the NP core was observed even for samples after exposure to air. From the comparison of HR-TEM experimental images with theoretical simulations, it was found that the Ni NP core has a regular multitwinned icosahedral structure, composed of single-crystal tetrahedra with (111) faces. The NiO phase is clearly observed forming islands on the NP surface.

STEM_CELL: A software tool for electron microscopy. Part 2 analysis of crystalline materials

A new graphical software (STEM_CELL) for analysis of HRTEM and STEM-HAADF images is here introduced in detail. The advantage of the software, beyond its graphic interface, is to put together different analysis algorithms and simulation (described in an associated article) to produce novel analysis methodologies. Different implementations and improvements to state of the art approach are reported in the image analysis, filtering, normalization, background subtraction. In particular two important methodological results are here highlighted: (i) the definition of a procedure for atomic scale quantitative analysis of HAADF images, (ii) the extension of geometric phase analysis to large regions up to potentially 1μm through the use of under sampled images with aliasing effects.