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Significance Nanotechnology and neurobiology combined efforts might succeed in the design of hybrid microsystems that, once functionally integrated into the nervous tissue, might help in healing the injured spinal cord. A substantial challenge in this area is the development of structural scaffolds favoring spinal cord reconstruction. The future success of such smart devices resides also in the use of nanomaterials exploiting spinal microenvironment physical properties, such as mechanical and electrical ones, and their potential in promoting axonal regeneration. We synthesized an artificial scaffold based on nanomaterials with the necessary characteristics to guide axonal rewiring. The translational potential of introducing physics rules to neural tissue repair strategies was tested by implanting such a scaffold in spinal cord injury animal models., The regrowth of severed axons is fundamental to reestablish motor control after spinal-cord injury (SCI). Ongoing efforts to promote axonal regeneration after SCI have involved multiple strategies that have been only partially successful. Our study introduces an artificial carbon-nanotube based scaffold that, once implanted in SCI rats, improves motor function recovery. Confocal microscopy analysis plus fiber tracking by magnetic resonance imaging and neurotracer labeling of long-distance corticospinal axons suggest that recovery might be partly attributable to successful crossing of the lesion site by regenerating fibers. Since manipulating SCI microenvironment properties, such as mechanical and electrical ones, may promote biological responses, we propose this artificial scaffold as a prototype to exploit the physics governing spinal regenerative plasticity.

International audience; Graphene (Gr) is known to be an excellent barrier preventing atoms and molecules to diffuse through it. This is due to the carbon atom arrangement in a two-dimensional (2D) honeycomb structure with a very small lattice parameter thus forming an electron cloud that prevents atoms and molecules crossing. Nonetheless at high an-nealing temperatures, intercalation of atoms through graphene occurs, opening the path for formation of vertical heterojunctions constituted of two-dimensional layers. In this paper, we report on the ability of silicon atoms to penetrate the graphene network, fully epitaxially grown on a Ni(111) surface, even at room temperature. Our scanning tunneling microscopy (STM) experiments show that the presence of defects like vacancies and disloca-tions in the graphene lattice favor the Si atoms intercalation, thus forming two-dimensional, flat and disordered islands below the Gr layer. Ab-initio molecular dynamics calculations confirm that Gr defects are necessary for Si intercalation at room temperature and show that: i) a hypothetical intercalated silicene layer cannot be stable for more than 8 ps and ii) the corresponding Si atoms completely lose their in-plane order resulting in a random planar distribution and form strong covalent bonds with Ni atoms.

A comprehensive picture of the initial stages of silicene growth on graphite is drawn. Evidence is shown that quasiparticle interferences play a crucial role in the formation of the observed silicene configurations. We propose, on one hand, that the charge modulations caused by those quantum interferences serve as templates and guide the incoming Si atoms to self-assemble to the unique $$\left( {\sqrt 3 \times \sqrt 3 } \right)$$ R30° honeycomb atomic arrangement. On the other hand, their limited extension limits the growth to about 150 Si atoms under our present deposition conditions. The here proposed electrostatic interaction finally explains the unexpected stability of the observed silicene islands over time and with temperature. Despite the robust guiding nature of those quantum interferences during the early growth phase, we demonstrate that the window of experimental conditions for silicene growth is quite narrow, making it an extremely challenging experimental task. Finally, it is shown that the experimentally observed three-dimensional silicon clusters might very well be the simple result of the end of the silicene growth resulting from the limited extent of the quasi-particle interferences.

The deposition of calcium fluoride (CaF2) on Si(111) at temperatures above 570 °C has been studied with scanning tunneling microscopy. At such temperatures, triangular calcium fluoride islands are formed both on terraces and along the phase domain boundaries of the (7 × 7) reconstruction of the Si(111) substrate. In addition to the formation of islands, we observe that CaF2 molecules react with the substrate inducing large areas of its surface to reconstruct into (√3 × √3) and c(2 × 4) phases. Upon annealing at 600 °C, the abovementioned areas of (√3 × √3) and c(2 × 4) turn into the stable (3 × 1) phase upon desorption of fluorine. Calcium fluoride islands are stable at this temperature. Depositions of calcium fluoride performed with Si substrate kept at higher temperature, namely at 680 °C, lead directly to the formation of (3 × 1) phase due to the complete desorption of fluorine, without passing through the formation of the metastable (√3 × √3) and c(2 × 4) phases. If CaF2/Si(111) is brought at even higher temperatures, Ca also starts desorbing and the (7 × 7)-Si(111) reconstruction can eventually be restored.

A dodecapeptide (AMRKLPDAPGMH) functionalized with a tetramethylrhodamine (TAMRA) chromophore at the N-terminus was immobilized on nanocrystalline TiO2. The optical and binding properties of the peptide layer immobilized on the titania surface were characterized by UV–vis absorption, steady-state fluorescence and X-ray photoelectron spectroscopies. Circular Dichroism experiments and Molecular Mechanics calculations showed that the predominant conformation populated by the peptide scaffold brings Arg3, Lys4 and Asp7 in the correct position for linking the TiO2 surface. Photocurrent generation experiments were therefore carried out to determine the photon-to-current conversion efficiency (IPCE) of a Grätzel-like Dye Sensitized Solar Cell (DSSC), the photoactive unit of which is formed by TAMRA-AMRKLPDAPGMH/TiO2. The measured IPCE amounted to 0.65%, a value that is definitely low, but superior to those previously reported for similar bioinspired DSSCs. This result can be ascribed to the light-harvesting properties of the TAMRA chromophore and to the unique structural properties of the peptide spacer. © 2017 Elsevier B.V.

In this work a new, simple and green protocol to introduce a limited content of silanol groups on the surface of an hydrophobic diatomite, in order to be slightly hydrophilic and susceptible to be silanized by bifunctional, sulfur-containing organosilanes for rubber applications, is proposed. The chemical modification was carried out at 85 °C in a solution of H 2 O:NaOH:H 2 O 2 . The modified diatomite was then silanized with bis(triethoxysilylpropyl) disulfide by a procedure that does not involve toxic solvent. Morphological features and elemental composition of diatomite were investigated by Field emission scanning electron microscopy coupled with Energy dispersive X-ray spectroscopy. The surface modification and silanization process were assessed by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Diatomite was composed by micrometric frustules from different diatom species with pore size ranging from 25 nm to 1 μm. The spectroscopic characterizations confirmed the surface modification of diatomite with some silanols that acted as sites for silanization reaction. The silanized diatomite and the untreated one were used as filler in unvulcanized solvent-cast SBR films in order to verify that the modification does not negatively affect the polymer/filler interface and as consequence the mechanical properties. Mechanical properties of the realized samples were assessed by uniaxial tensile tests. Films filled with 10 wt% of diatomite (untreated or silanized) showed an increase of Elastic Modulus about of 50% and a decrease of the strain at break with respect to SBR samples, while the tensile strength was not significantly affected by the diatomite addition. SEM images of fracture surfaces of tested specimens showed a fine dispersion of both untreated and silanized diatomite in the polymeric matrix and the achieving of a good interfacial adhesion SBR/fillers. The silanized diatomite, as it is potentially able to bind chemically to elastomeric molecules during vulcanization process, could be used in rubber compounds as semi-reinforcing filler.

In this work, the authors investigated MoO3 films with thickness between 30 nm and 1 μm grown at room temperature by solid phase deposition on polycrystalline Cu substrates. Atomic force microscopy, scanning electron microscopy, and scanning tunneling microscopy revealed the presence of a homogenous MoO3 film with a “grainlike” morphology, while Raman spectroscopy showed an amorphous character of the film. Nanoindentation measurements evidenced a coating hardness and stiffness comparable with the copper substrate ones, while Auger electron spectroscopy, x-ray absorption spectroscopy, and secondary electron spectroscopy displayed a pure MoO3 stoichiometry and a work function ΦMoO3 = 6.5 eV, 1.8 eV higher than that of the Cu substrate. MoO3 films of thickness between 30 and 300 nm evidenced a metallic behavior, whereas for higher thickness, the resistance–temperature curves showed a semiconducting character.In this work, the authors investigated MoO3 films with thickness between 30 nm and 1 μm grown at room temperature by solid phase deposition on polycrystalline Cu substrates. Atomic force microscopy, scanning electron microscopy, and scanning tunneling microscopy revealed the presence of a homogenous MoO3 film with a “grainlike” morphology, while Raman spectroscopy showed an amorphous character of the film. Nanoindentation measurements evidenced a coating hardness and stiffness comparable with the copper substrate ones, while Auger electron spectroscopy, x-ray absorption spectroscopy, and secondary electron spectroscopy displayed a pure MoO3 stoichiometry and a work function ΦMoO3 = 6.5 eV, 1.8 eV higher than that of the Cu substrate. MoO3 films of thickness between 30 and 300 nm evidenced a metallic behavior, whereas for higher thickness, the resistance–temperature curves showed a semiconducting character.

Highly oriented pyrolitic graphite (HOPG) is an inert substrate with a structural honeycomb lattice, well suited for the growth of two-dimensional (2D) silicene layer. It was reported that when Si atoms are deposited on HOPG surface at room temperature, they arrange in two configurations: silicene nanosheets and three dimensional clusters. In this work we demonstrate, by using scanning tunneling microscopy (STM) and Raman spectroscopy, that a third configuration stabilizes in the form of Si 2D nanosheets intercalated below the first top layer of carbon atoms. The Raman spectra reveal a structure located at 538 cm$^{-1}$ which we ascribe to the presence of sp$^2$ Si hybridization. Moreover, the silicon deposition induces several modifications in the graphite D and G Raman modes, which we interpret as an experimental evidence of the intercalation of the silicene nanosheets. The Si atom intercalation at room temperature takes place at the HOPG step edges and it detaches only the outermost graphene layer inducing a strong tensile strain mainly concentrated on the edges of the silicene nanosheets. Theoretical calculations of the structure and energetic viability of the silicene nanosheets, of the strain distribution on the outermost graphene layer and its influence on the Raman resonances support the STM and Raman observations., 18 pages, 9 figures, 2 tables

The microwave conductivity and permittivity of both single-walled and multi-walled carbon nanotube (SWCNT and MWCNT) sponges were measured while compressing the samples. Compression leads to a huge variation of the absorptance, reflectance, and transmittance of the samples. The dependence of the microwave conductivity on the sponge density follows a power-law relation with exponents 1.7 ± 0.1 and 2.0 ± 0.2 for MWCNT and SWCNT sponges, respectively. These exponents can be decreased slightly by the addition of a non-conducting component which partly electrically separates adjacent tubes within the samples. The conductivity of MWCNT sponge was measured in the terahertz range while heating in air from 300 to 513 K and it increased due to an increase of a number of conducting channels in MWCNTs.

Carbon spheres of nanometric dimension are known since the first studies on the synthesis of fullerenes. Their shape originates from the curvature of a carbon sheet similar to fullerenes, but with numerous graphitic rings that regulate the inside structure and the formation of open edges at the surface. This paper focuses on the structural and electronic characterization of carbon spheres obtained from a chemical vapor deposition synthesis process. Two different sets of samples are analyzed in detail, in particular, electron microscopies and Raman spectroscopy help understanding the morphology and the graphitic-sp2 arrangement of the carbon atoms in the architectures. In addition, the iron catalyst used during the reaction process confers the carbon spheres a ferromagnetic response at room temperature. Therefore, both the structural properties of the samples and the active contribution of iron mark the difference in the measured photoresponse as well as in the electrochemical behavior. The X-ray photoelectron spectroscopy study addresses these points by giving information on the composition and the iron chemical state in the assembly. The collected results underline the advantages offered by this nanomaterial for sustainable applications.

Herein, we report the synthesis of several magnetic carbon structures starting from spheres (CSs) to more elongated structures to get tubes and fibers by customizing chemical vapour deposition parameters. These CSs-based products, ranging from nano-to micro-size, were investigated by morphological point of view using scanning electron microscopy, energy dispersive x-ray spectroscopy, and Raman spectroscopy. These carbon structures were combined with screen-printed electrodes highlighting their electrochemical effectiveness towards the detection of several species, i.e. ferricyanide, ascorbic acid, dopamine, cysteine, serotonin, and NADH. The presence of iron nuclei within the carbonaceous lattices, besides having improved the electrochemical performances at the printed electrodes, might confer these CSs-based structures a future application in the field of remediation/sensing. Herein, some preliminary applications were provided showing that these materials can be easily employed to collect species and, successively, coupled with printed electrochemical sensors.

Carbon spheres of nanometric dimension are known since the first studies on the synthesis of fullerenes. Their shape originates from the curvature of a carbon sheet similar to fullerenes, but with numerous graphitic rings that regulate the inside structure and the formation of open edges at the surface. This paper focuses on the structural and electronic characterization of carbon spheres obtained from a targeted chemical vapor deposition synthesis process. Two different set of samples are analyzed in detail, in particular, the electron microscopies and Raman spectroscopy help understanding the morphology and the graphitic-sp2 arrangement of the carbon atoms in the architectures. In addition, the iron catalyst used during the reaction process confers the carbon spheres a ferromagnetic response at room temperature. Therefore, both the structural properties of the samples and the active contribution of iron mark the difference in the measured photoresponse as well as in the electrochemical behavior. The X-ray photoelectron spectroscopy study addresses these points by giving information on the composition and the iron chemical state in the assembly. The collected results underline the advantages offered by this synthesis route and the properties of the carbon spheres as active nanomaterial for sustainable applications.

Meso-tetraphenylporphyrin connected with a ferrocene molecule in the beta-position of the macrocycle through a triple carbon@carbon bond has been bound to carbon spheres using the Prato@Maggini reaction. The ethynyl or/and phenylene ethynylene subunits were chosen as a linking bridge to give a high conjugation degree between the donor (i. e., ferrocene), the photoactive compound (i. e., porphyrin), and the acceptor (i. e., carbon spheres). The molecular bridges have been directly linked to the beta-pyrrole positions of the porphyrin ring, generating a new example of a long-range donor@acceptor system. Steady-state fluorescence studies together with Raman and XPS measurements helped understanding the chemical and physical properties of the porphyrin ring in the new adduct. The spectroscopic characteristics were also compared with those obtained from a similar compound bearing fullerene instead of carbon spheres. &nbsp

Here we present for the first time polymer solar cells that incorporate biological material that show state of the art efficiencies in excess of 8%. The performance of inverted polymer solar cells was improved significantly after deposition of ZnO nanoparticles (ZnO-NPs) together with a thin deoxyribonucleic acid nanolayer and used as an electron extraction layer (EEL). The ZnO-NPs/DNA double layer improved the rectifying ratio, shunt resistance of the cells as well as lowering the work function of the electron-collecting contact. Importantly, the ZnO-NPs/DNA bilayer enhanced the power conversion efficiency of cells considerably compared to cells with EELs made of only DNA (improvement of 56% in relative terms) or only ZnO-NPs (improvement of 19% in relative terms) reaching a best power conversion efficiency of 8.5%. The ZnO-NPs/DNA double layer cells also outperformed ones made with one of the most efficient previous synthetic composite EELs (i.e. ZnO/PEIE(poly(ethyleneimine)-ethoxylated)). Since all fabrication procedures were carried out at low (

In this paper, we show that it is possible to synthesize carbon-based three-dimensional networks by adding sulfur, as growth enhancer, during the synthesis process. The obtained material is self-supporting and consists of curved and interconnected carbon nanotubes and to lesser extent of carbon fibers. Studies on the microstructure indicate that the assembly presents a marked variability in the tube external diameter and in the inner structure. We study the relationship between the observed microscopic properties and some potential applications. In particular, we show that the porous nature of the network is directly responsible for the hydrophobic and the lipophilic behavior. Moreover, we used a cut piece of the produced carbon material as working electrode in a standard electrochemical cell and, thus, demonstrating the capability of the system to respond to incident light in the visible and near-ultraviolet region and to generate a photocurrent.

Self-assembled hierarchical solid surfaces are very interesting for wetting phenomena, as observed in a variety of natural and artificial surfaces. Here, we report single-walled (SWCNT) and multi-walled carbon nanotube (MWCNT) thin films realized by a simple, rapid, reproducible, and inexpensive filtration process from an aqueous dispersion, that was deposited at room temperature by a dry-transfer printing method on glass. Furthermore, the investigation of carbon nanotube films through scanning electron microscopy (SEM) reveals the multi-scale hierarchical morphology of the self-assembled carbon nanotube random networks. Moreover, contact angle measurements show that hierarchical SWCNT/MWCNT composite surfaces exhibit a higher hydrophobicity (contact angles of up to 137{\deg}) than bare SWCNT (110{\deg}) and MWCNT (97{\deg}) coatings, thereby confirming the enhancement produced by the surface hierarchical morphology., Comment: 7 pages, 5 figures, This article is part of the Thematic Series "Self-assembly of nanostructures and nanomaterials"

A helical hexapeptide was designed to link in a rigid parallel orientation to a gold surface. The peptide sequence of the newly synthesized compound is characterized by the presence of two 4-amino-1,2-dithiolane-4-carboxylic acid (Adt) residues (positions 1 and 4) to promote a bidentate interaction with the gold surface, two L-Ala residues (positions 2 and 5) and two-aminoisobutyric acid (Aib) residues (positions 3 and 6) to favor a high population of the 3(10)-helix conformation. Furthermore, a ferrocenoyl (Fc) probe was inserted at the N-terminus to investigate the electronic conduction properties of the peptide. X-Ray photoelectron spectroscopy and scanning tunneling microscopy techniques were used to characterize the binding of the peptide to the gold surface and the morphology of the peptide layer, respectively. Several electrochemical (cyclic voltammetry, chronoamperometry, square wave voltammetry) techniques were applied to analyze the electrochemical activity of the Fc probe, along with the influence of the peptide 3D-structure and the peptide layer morphology on electron transfer processes.

The sponges made of multi-walled carbon nanotubes (CNT) demonstrate tunable electromagnetic response properties in the microwave range (27–36 GHz) governed by their mechanical deformation. The higher the applied stress, the denser the sponge, the more reflective it is in the Ka-band. The microwave effective conductivity of the CNT network macrostructure was proved to be linearly increased with its density.

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 sp

Large nanostructures of silicene have been successfully grown on graphene covered 6H-SiC (0001) substrates. The graphene plays an important role to obtain honeycomb structures of silicon in the sp2 configuration and acts as an ideal template for 2D materials. The scanning tunneling microscopy images showed nanosheets of silicene with a very small buckling among the Si atoms. Our scanning tunneling spectroscopy confirmed the metallic character of the deposited silicene in excellent agreement with band structure calculations that also exhibit the presence of Dirac cones.

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.

Films of multiwall carbon nanotubes (CNTs), arranged on Si/SiO2 substrates, are used as templates for Nb films with thickness in the range 3–50 nm deposited by sputtering. The resulting aggregates show normal state and superconducting properties similar to those observed in networks of superconducting nanowires (SNW) obtained by other methods. Decreasing the Nb thickness, when the normal state resistance becomes larger than the quantum resistance, a superconductor-insulator transition is observed. Moreover, thermally activated phase slips in thicker samples, evolving in quantum phase slips in thinner nanowires, are observed in the superconducting state. The experimental results indicate that the template method based on CNTs is a promising alternative to the much more expensive nanolithography techniques for obtaining SNWs. Even more important, they indicate CNT films as versatile elements in nanostructured electronic devices.

Multi-walled carbon nanotube (MWCNT) films form efficient heterojunction solar cells with n-type crystalline silicon (n-Si), due to their superior optical and electrical properties. Here, we report air-stable photovoltaic devices with record photoconversion efficiency of 10%. We realized thin films consisting of MWCNTs arranged in semitransparent random networks deposited on n-Si substrates by a simple, rapid, reproducible, and inexpensive vacuum filtration process at room temperature. Such heterojunctions favor high and broadband carrier photogeneration, extending the Si spectral response from near infrared to near ultraviolet range; charge dissociation of ultrafast hot carriers [1]; transport of electrons through n-Si and high-mobility [2] holes through the MWCNT percolative network. Furthermore, by varying the MWCNT film thickness, it is possible tailoring its optical and electrical properties, therefore the overall device optoelectronic features. These results not only pave the way for low-cost, efficient, and broadband photovoltaics, but also are promising for the development of MWCNT-based optoelectronic applications.

Multidentate binding of two helical hexapeptides to a gold surface was obtained by introducing in the peptide chain a non ribosomial amino acid, i.e. the 4-amino-1,2-dithiolane-4-carboxylic acid (Adt) residue, a C α -tetrasubstituted α-amino acid bearing a heterocyclic side chain characterized by a disulfide group. The two peptides, mainly formed by strongly helicogenic C α -tetrasubstituted α-amino acids, were both functionalized at the N-terminus by a ferrocenoyl (Fc) group, but differ in the number of Adt residues included in the peptide chain: the former (Fc6Adt2) contains two Adt residues at positions 1 and 4, while its analog (Fc6Adt1) contains a single Adt at position 4, since the Adt at position 1 is substituted by an α-amino isobutyric acid (Aib) residue. This peptide design allowed us to explore the different electrochemical properties and morphologies shown by the two peptide layers immobilized on a gold surface by two (Fc6Adt2) or a single (Fc6Adt1) bidentate linker, respectively. The electrochemical activity of the ferrocenoyl probe embedded in the peptide film was characterized by cyclic voltammetry, chronoamperometry and square wave voltammetry, while the binding and the morphology of the peptide layers were studied by X-ray photoelectron spectroscopy (XPS) and ultra high vacuum scanning tunneling microscopy (UHV-STM), respectively. Significant differences were observed in the electron transfer (ET) properties of the two peptides investigated, which emerge from the diverging morphology achieved by the peptide layers on the gold surface. It was found that while a standing-up configuration of the peptide layer, realized by a single bidentate linkage, maximizes the ET efficiency, a lying down configuration (two Adt linkages) allows for precise positioning of Fc in the proximity of a gold surface.

Deoxyribonucleic acid (DNA) was successfully incorporated as a nanolayer between the bottom indium tin oxide (ITO) transparent electrode and the photoabsorbing film in a polymer solar cell. Upon film optimization and analyses with scanning tunneling spectroscopy/currents, we demonstrate that a 1–6 nm thick DNA stratum functions as an effective electron-extracting layer, leading to strong improvements in rectifying behavior (by 2 orders of magnitude with rectifying ratios reached larger than 103) and in photovoltaic parameters like the open-circuit voltage (VOC from 0.39 to 0.73 V) and power conversion efficiencies (PCEs from ∼2 to ∼5%). The results show that DNA is a very ductile nanomaterial for electronic purposes, paving the way for future exploration in photovoltaic devices combining its electron-extracting properties with its functional and self-assembly behavior. Furthermore, solar cell devices were completely processed at room temperature, and DNA was cast from ecofriendly solvents such as water an...

Negative differential resistance (NDR), for which the current is a decreasing function of the voltage, has been observed in the current–voltage curves of several types of structures. We measured tunnelling current and NDR by illuminating large area heterojunction obtained by growing Multi Wall Carbon Nanotubes on the surface of n-doped Silicon substrate. In the absence of light, the current flow is null until a junction threshold of about 2.4 V is reached, beyond which the dark current flows at room temperature with a very low intensity of few nA. When illuminated, a current of tens nA is observed at a drain voltage of about 1.5 V. At higher voltage the current intensity decreases according to a negative resistance of the order of MΩ. In the following we report details of tunneling photodiode realized and negative resistance characteristics.

We have taken advantage of the native surface roughness and the iron content of AISI-316 stainless steel to grow multiwalled carbon nanotubes (MWCNTs) by chemical vapour deposition without the addition of an external catalyst. The structural and electronic properties of the synthesized carbon nanostructures have been investigated by a range of electron microscopy and spectroscopy techniques. The results show the good quality and the high graphitization degree of the synthesized MWCNTs. Through energy-loss spectroscopy we found that the electronic properties of these nanostructures are markedly different from those of highly oriented pyrolytic graphite (HOPG). Notably, a broadening of the π-plasmon peak in the case of MWCNTs is evident. In addition, a photocurrent was measured when MWCNTs were airbrushed onto a silicon substrate. External quantum efficiency (EQE) and photocurrent values were reported both in planar and in top-down geometry of the device. Marked differences in the line shapes and intensities were found for the two configurations, suggesting that two different mechanisms of photocurrent generation and charge collection are in operation. From this comparison, we are able to conclude that the silicon substrate plays an important role in the production of electron–hole pairs.

We report on the multiwall carbon nanotube application as energy conversion material to fabricate thin film solar cells, with nanotubes acting as photogeneration sites as well as charge separators, collectors and carrier transporters. The device consists of a semitransparent thin film of nanotubes coating a n-type crystalline silicon substrate. Under illumination electron-hole (e-h) pairs, generated in the nanotubes and in the silicon substrate underneath, are split and charges are transported through the nanotubes (electrons) and the n-Si (holes). We found that a suitable thickness of the nanotube thin film, high density of Schottky junctions between nanotubes and n-Si and lowest number of nanotube walls are all fundamental parameters to improve the device incident photon to electron conversion efficiency. Multiwall carbon nanotubes have been synthesized by chemical vapour deposition in an ultra high vacuum chamber by evaporating a given amount of iron at room temperature and then exposing the substrate kept at 800 degrees C at acetylene gas. The amount of deposited iron is found to directly affect the nanotube size distribution (inner and outer diameter) and therefore the number of walls of the nanotubes.

We report on the generation of photocurrent in the visible and ultraviolet range from planar devices built from the Ge nanocrystals grown on a heavy n-doped Si(001) substrate covered with 5 nm thick thermally grown SiO2. These Ge nanostructures/SiO2/n(+)-Si devices are shown to generate photocurrent with an Incident-Photon-to-electron Conversion Efficiency (IPCE) spectral range depending on the Ge nanocrystals size. The increase of the IPCE value of our devices in the 350-600 nm range correlates well with the absorbance of Ge.

International audience; Multi wall carbon nanotubes (MWCNTs) were grown on a stainless steel (SS) sheet by chemical vapor deposition without the addition of external metal catalyst. We found that the key for highly efficient growth includes the nanoscale roughness of the SS surface, as shown by scanning tunneling microscopy, that acts as catalyst/template in the nanotube formation. Raman spectroscopy and electron microscopy were used to check the nature and quality of the synthesized nanotubes. We conclude that stainless steel favors a base-growth mechanism. Transmission electron energy loss spectroscopy performed on single metallic particles found inside the nanotubes clarified the atomic nature of the catalytic particles supplied by the steel. Only unoxidized iron was found and no traces of nickel and chromium were detected. In addition, the SS substrate has been used for a second growth process after carefully removing the synthesized CNTs, proving that a continuous production of CNTs from the same substrate is achievable.

The inclusion of carbon nanotubes in polymer matrix has been proposed to enhance the polymer’s physical and electrical properties. In this study, microscopic and spectroscopic techniques are used to investigate the interaction between poly(3-hexylthiophene) (P3HT) and nanotubes and the reciprocal modification of physical properties. The presence of P3HT-covered nanotubes dispersed in the polymer matrix has been observed by atomic force microscopy and transmission electron microscopy. Then, the modification of P3HT optical properties due to nanotube inclusion has been evidenced with spectroscopic techniques like absorption and Raman spectroscopy. The study is completed with detailed nanoscale analysis by scanning probe techniques. The ordered self assembly of polymer adhering on the nanotube is unveiled by showing an example of helical wrapping of P3HT. Scanning tunneling spectroscopy study provides information on the electronic structure of nanotube-polymer assembly, revealing the charge transfer from P3HT to the nanotube.

We show that when a soft polymer like Poly(3-hexyl-thiophene) wraps multiwall nanotubes by coiling around the main axis, a localized deformation of the nanotube structure is observed. High resolution transmission electron microscopy shows that radial compressions of about 4% can take place, and could possibly lead to larger interlayer distance between the nanotube inner walls and reduce the innermost nanotube radius. The mechanical stress due to the polymer presence was confirmed by Raman spectroscopic observation of a gradual upshift of the carbon nanotube G-band when the polymer content in the composites was progressively increased. Vibrational spectroscopy also indicates that charge transfer from the polymer to the nanotubes is responsible for a peak frequency relative downshift for high P3HT-content samples. Continuously acquired transmission electron microscopy images at rising temperature show the MWCNT elastic compression and relaxation due to polymer rearrangement on the nanotube surface.

Controlled synthesis of carbon nanotubes (CNTs) is highly desirable for nanoelectronic applications. To date, metallic catalyst particles have been deemed unavoidable for the nucleation and growth of any kind of CNTs. Ordered arrays of nanotubes have been obtained by controlled deposition of the metallic catalyst particles. However, the presence of metal species mixed with the CNTs represents a shortcoming for most electronic applications, as metal particles are incompatible with silicon semiconductor technology. In the present paper we report on a metal-catalyst-free synthesis of CNTs, obtained through Ge nanoparticles on a Si(001) surface patterned by nanoindentation. By using acetylene as the carbon feed gas in a low-pressure Chemical Vapor Deposition (CVD) system, multi-walled carbon nanotubes (MWNT) have been observed to arise from the smallest Ge islands. The CNTs and the Ge three-dimensional structures have been analysed by SEM, EDX and AFM in order to assess their elemental features and properties. EDX and SEM results allow confirmation of the absence of any metallic contamination on the surface, indicating that the origin of the CNT growth is due to the Ge nanocrystals.

In this work we show that a sizeable enhancement in the photocurrent over the visible and near ultraviolet energy range can be obtained from multi-wall carbon nanotubes when decorated with Cu-nanoparticles. The result has been obtained both from electrochemical and solid state cells measurements. The photoactive metal nanoparticles do not change the intrinsic ability of multi-wall carbon nanotubes to behave as an efficient low dimensional media for generating e–h carriers. This result further confirms that multi wall carbon nanotubes can be used in photovoltaic nano-devices and solar energy conversion applications.

The photocurrent generation of nanometric Ge droplets has been investigated by using electrochemical measurements. Dots have been grown by annealing Ge layers of different nominal thicknesses (ranging from 0.5 to 5 nm) deposited on clean SiO2 surface at room temperature. The photocurrent signals for the largest dots show features, which can be ascribed to the Ge nanocrystals direct electronic transitions. Only in the case of 0.5 nm Ge film a broad and intense feature at 2.4 eV has been observed while the peaks at higher energy result to be dramatically reduced. Since this last sample is characterized by (5±1) nm nanodots size (the smallest among the measured samples) the appearance of this broad band in the photocurrent active spectrum can be ascribed to quantum confinement effect.

Here, we investigate the thickness of single-walled (SWCNT) and multi-walled carbon nanotube (MWCNT) random network films by angle-resolved X-ray photoemission spectroscopy. Furthermore, we estimate the absorption coefficient of carbon nanotube (CNT) films through the Lambert–Beer law, by measuring film optical spectra. Moreover, the knowledge of the absorption coefficient provides an easier, reliable, and faster method of investigation for generic CNT film thickness. In addition, the absorption coefficient leads to the information of the absorption length for SWCNT and MWCNT films, which is a physical quantity of fundamental interest for optoelectronic applications, such as light emitting diodes, photovoltaics, and in general light absorbers.

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.

A significant resonant tunneling effect has been observed under the 2.4 V junction threshold in a large area, carbon nanotube–silicon (CNT–Si) heterojunction obtained by growing a continuous layer of multiwall carbon nanotubes on an n-doped silicon substrate. The multiwall carbon nanostructures were grown by a chemical vapor deposition (CVD) technique on a 60 nm thick, silicon nitride layer, deposited on an n-type Si substrate. The heterojunction characteristics were intensively studied on different substrates, resulting in high photoresponsivity with a large reverse photocurrent plateau. In this paper, we report on the photoresponsivity characteristics of the device, the heterojunction threshold and the tunnel-like effect observed as a function of applied voltage and excitation wavelength. The experiments are performed in the near-ultraviolet to near-infrared wavelength range. The high conversion efficiency of light radiation into photoelectrons observed with the presented layout allows the device to be used as a large area photodetector with very low, intrinsic dark current and noise.

We first investigate the spontaneous formation of nanometric and highly dense (∼3×10 12 cm −2 ) Ge droplets on SiO 2 /Si(0 0 1) by scanning tunnelling microscopy and spectroscopy. Ge dots are grown using a two-step process: first, Ge deposition on the clean SiO 2 surface at room temperature (RT) and second, thermal annealing at 500 °C. Ge dots appear free of germanium oxides. Then we show the ordering of Ge nanocrystals (NCs) on SiO 2 /Si(0 0 1) substrates patterned by focused ion beam (FIB). Lateral ordering of the ultra-dense Ge nanodots was achieved by the combination of the following technological steps: (a) use of a FIB to create ordered two-dimensional (2D) arrays of regular holes on a field oxide on the silicon substrate, (b) chemical cleaning and restoring of the Si surface in the holes, (c) further oxidation to transfer the pattern from the field oxide to the silicon substrate, (d) removal of the field oxide and thermal re-oxidation of the sample in order to create a tunnelling oxide of homogeneous thickness on the patterned silicon surface and (e) self-assembly of the 2D arrays of Ge dots on the patterned tunnelling oxide. We show that Ge NCs are ordered in the FIB holes whatever is their dimension/density.

Transmission electron microscopy (TEM) and electron energy loss near-edge structure (EELNES) revealed the presence of mostly non-oxidised silicon tubular structures among the reaction products synthesized by gas phase condensation technique. Scanning tunneling microscopy (STM) showed a hexagonal atomic arrangement for straight ones. The presence of Y-, T-branched and coiled tubular structure, like in carbon nanotubes, suggests a partially sp2 hybridization. Reflection energy loss measurements confirmed the presence of thin tubular structures and gave hint of sp3 bonds.

A novel hexapeptide was functionalized at the N-terminus by a lipoyl group for binding to gold substrates. Owing to the high content of α-aminoisobutyric acid residues, the peptide adopts a rigid helical conformation despite the shortness of its main chain. Binding of the peptide to gold was investigated by quartz crystal microbalance, cyclic voltammetry, X-ray photoelectron spectroscopy, and scanning tunneling microscopy under ultra-high vacuum conditions. Scanning tunneling microscopy experiments revealed that the peculiar self-assembly properties of this short helical peptide determine the complex morphology of the monolayer, showing ‘stripes’, i.e. peptide aggregates horizontally layered on the gold surface, and ‘holes’, i.e. Au vacancy islands coated by the peptide monolayer.

We report on a new photodetector fabricated using carbon nanostructures grown on a silicon substrate. This device exhibits low noise, a good conversion efficiency of photons into electrical current and a good signal linearity in a wide range of radiation wavelengths ranging from ultraviolet to infrared at room temperature. The maximum quantum efficiency of 37% at 880 nm has been measured without signal amplification. Such innovative devices can be easily produced on large scales by Chemical Vapour Deposition (CVD) through a relatively inexpensive chemical process, which allows large sensitive areas from a few mm2 up to hundreds of cm2 to be covered.