Maurizio De Crescenzi

Regioregular poly(3-hexyl-thiophene) helical self-organization on carbon nanotubes

Mixtures of regioregular poly(3-hexyl-thiophene) (rrP3HT) and multiwall carbon nanotubes have been investigated by scanning tunneling microscopy in ultrahigh vacuum. Carbon nanotubes covered by rrP3HT have been imaged and analyzed, providing a clear evidence that this polymer self-assembles on the nanotube surface following geometrical constraints and adapting its equilibrium chain-to-chain distance. Largely spaced covered nanotubes have been analyzed to investigate the role played by nanotube chirality in the polymer wrapping, evidencing strong rrP3HT interactions along well defined directions.

Light harvesting with multiwall carbon nanotube/silicon heterojunctions

We report on a significant photocurrent generation from a planar device obtained by coating a bare n doped silicon substrate with a random network of multiwall carbon nanotubes (MWCNTs). This MWCNT/n-Si hybrid device exhibits an incident photon to current efficiency reaching up to 34% at 670 nm. We also show that MWCNTs covering a quartz substrate still exhibit photocurrent, though well below than that of the MWCNTs coating the silicon substrate. These results suggest that MWCNTs are able to generate photocurrent and that the silicon substrate plays a fundamental role in our planar device. The former effect is particularly interesting because MWCNTs are generally known to mimic the electronic properties of graphite, which does not present any photocurrent generation. On the basis of theoretical calculations revealing a weak metallic character for MWCNTs, we suggest that both metallic and semiconducting nanotubes are able to generate e-h pairs upon illumination. This can be ascribed to the presence of van Hove singularities in the density of states of each single wall carbon nanotube constituting the MWCNT and to the low density of electrons at the Fermi level. Finally, we suggest that though both MWCNTs and Si substrate are involved in the photocurrent generation process, MWCNT film mainly acts as a semitransparent electrode in our silicon-based device.

Composition of Ge — Si – islands in the growth of Ge on Si — 111 – by x-ray spectromicroscopy

The stoichiometry of Ge∕Si islands grown on Si(111) substrates at temperatures ranging from 460to560°C was investigated by x-ray photoemission electron microscopy (XPEEM). By developing a specific analytical framework, quantitative information on the surface Ge∕Si stoichiometry was extracted from laterally resolved XPEEM Si 2p and Ge 3d spectra, exploiting the chemical sensitivity of the technique. Our data show the existence of a correlation between the base area of the self-assembled islands and their average surface Si content: the larger the lateral dimensions of the 3D structures, the higher their relative Si concentration. The deposition temperature determines the characteristics of this relation, pointing to the thermal activation of kinetic diffusion processes.

Composition of Ge(Si) islands in the growth of Ge on Si(111)

X-ray photoemission electron microscopy (XPEEM) is used to investigate the chemical composition of Ge/Si individual islands obtained by depositing Ge on Si(111) substrates in the temperature range 460–560 °C. We are able to correlate specific island shapes with a definite chemical contrast in XPEEM images, at each given temperature. In particular, strained triangular islands exhibit a Si surface content of 5%–20%, whereas it grows up to 30%–40% for “atoll-like” structures. The island’s stage of evolution is shown to be correlated with its surface composition. Finally, by plotting intensity contour maps, we find that island centers are rich in Si.

Super-Hydrophobic Multi-Walled Carbon Nanotube Coatings for Stainless Steel

We have taken advantage of the native surface roughness and the iron content of AISI 316 stainless steel to directly grow multi-walled carbon nanotube (MWCNT) random networks by chemical vapor deposition (CVD) at low-temperature (1000°C) without the addition of any external catalysts or time-consuming pre-treatments. In this way, super-hydrophobic MWCNT films on stainless steel sheets were obtained, exhibiting high contact angle values (154°C) and high adhesion force (high contact angle hysteresis). Furthermore, the investigation of MWCNT films with scanning electron microscopy (SEM) reveals a two-fold hierarchical morphology of the MWCNT random networks made of hydrophilic carbonaceous nanostructures on the tip of hydrophobic MWCNTs. Owing to the Salvinia effect, the hydrophobic and hydrophilic composite surface of the MWCNT films supplies a stationary super-hydrophobic coating for conductive stainless steel. This biomimetical inspired surface not only may prevent corrosion and fouling, but also could provide low friction and drag reduction.

Multi-Fractal Hierarchy of Single-Walled Carbon Nanotube Hydrophobic Coatings

A hierarchical structure is an assembly with a multi-scale morphology and with a large and accessible surface area. Recent advances in nanomaterial science have made increasingly possible the design of hierarchical surfaces with specific and tunable properties. Here, we report the fractal analysis of hierarchical single-walled carbon nanotube (SWCNT) films realized by a simple, rapid, reproducible, and inexpensive filtration process from an aqueous dispersion, then deposited by drytransfer printing method on several substrates, at room temperature. Furthermore, by varying the thickness of carbon nanotube random networks, it is possible tailoring their wettability due to capillary phenomena in the porous films. Moreover, in order to describe the wetting properties of such surfaces, we introduce a two-dimensional extension of the Wenzel-Cassie-Baxter theory. The hierarchical surface roughness of SWCNT coatings coupled with their exceptional and tunable optical and electrical properties provide an ideal hydrophobic composite surface for a new class of optoelectronic and nanofluidic devices.

Poly(3-hexyl-thiophene) coil-wrapped single wall carbon nanotube investigated by scanning tunneling spectroscopy

Scanning tunneling spectroscopy was performed on a (15,0) single wall carbon nanotube partially wrapped by poly(3-hexyl-thiophene). On the bare nanotube section, the local density of states is in good agreement with the theoretical model based on local density approximation and remarkably is not perturbed by the polymer wrapping. On the coiled section, a rectifying current-voltage characteristic has been observed along with the charge transfer from the polymer to the nanotube. The electron transfer from poly(3-hexyl-thiophene) to metallic nanotube was previously theoretically proposed and contributes to the presence of the Schottky barrier at the interface responsible for the rectifying behavior.

3D meshes of carbon nanotubes guide functional reconnection of segregated spinal explants

Three-dimensional carbon nanotube frameworks favor spinal cord explant rewiring of motor outputs. In modern neuroscience, significant progress in developing structural scaffolds integrated with the brain is provided by the increasing use of nanomaterials. We show that a multiwalled carbon nanotube self-standing framework, consisting of a three-dimensional (3D) mesh of interconnected, conductive, pure carbon nanotubes, can guide the formation of neural webs in vitro where the spontaneous regrowth of neurite bundles is molded into a dense random net. This morphology of the fiber regrowth shaped by the 3D structure supports the successful reconnection of segregated spinal cord segments. We further observed in vivo the adaptability of these 3D devices in a healthy physiological environment. Our study shows that 3D artificial scaffolds may drive local rewiring in vitro and hold great potential for the development of future in vivo interfaces.

Formation of Silicene Nanosheets on Graphite

The extraordinary properties of graphene have spurred huge interest in the experimental realization of a two-dimensional honeycomb lattice of silicon, namely, silicene. However, its synthesis on supporting substrates remains a challenging issue. Recently, strong doubts against the possibility of synthesizing silicene on metallic substrates have been brought forward because of the non-negligible interaction between silicon and metal atoms. To solve the growth problems, we directly deposited silicon on a chemically inert graphite substrate at room temperature. Based on atomic force microscopy, scanning tunneling microscopy, and ab initio molecular dynamics simulations, we reveal the growth of silicon nanosheets where the substrate-silicon interaction is minimized. Scanning tunneling microscopy measurements clearly display the atomically resolved unit cell and the small buckling of the silicene honeycomb structure. Similar to the carbon atoms in graphene, each of the silicon atoms has three nearest and six second nearest neighbors, thus demonstrating its dominant sp2 configuration. Our scanning tunneling spectroscopy investigations confirm the metallic character of the deposited silicene, in excellent agreement with our band structure calculations that also exhibit the presence of a Dirac cone.

Pressure-dependent electrical conductivity of freestanding three-dimensional carbon nanotube network”

The dependence of electrical conductivity on compression of a freestanding three-dimensional carbon nanotube (CNT) network is investigated. This macrostructure is made of mm-long and entangled CNTs, forming a random skeleton with open pores. The conductivity linearly increases with the applied compression. This behaviour is due to increase of percolating pathways—contacts among neighbouring CNTs—under loads that is highlighted by in situ scanning electron microscopy analysis. The network sustains compressions up to 75% and elastically recovers its morphology and conductivity during the release period. The repeatability coupled with the high mechanical properties makes the CNT network interesting for pressure-sensing applications.