Scanning tunneling microscopy and Raman evidence of silicene nanosheets intercalated into graphite surfaces at room temperature.

Highly oriented pyrolytic graphite (HOPG) is an inert substrate with a structural honeycomb lattice, well suited for the growth of a two-dimensional (2D) silicene layer. It was reported that when Si atoms are deposited on the HOPG surface at room temperature, they arrange into 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 sp2 Si hybridization. Moreover, the silicon deposition induces several modifications in the graphite D and G Raman modes, which we interpret as 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 graphite 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 and of the strain distribution on the outermost graphite layer and its influence on the Raman resonances support the STM and Raman observations.

Single walled carbon nanotube/Si heterojunctions for high responsivity photodetectors.

Single walled carbon nanotube/n-Si (SWCNT/n-Si) hetero-junctions have been obtained by depositing SWCNT ultra-thin films on the surface of an n-Si substrate by dry transfer method. The as obtained junctions are photo sensitive in the measured wavelength range (300-1000 nm) and show zero bias responsivity and detectivity values of the order of 1 A W-1 and 1014 Jones respectively, which are higher than those previously observed in carbon based devices. Moreover, under on-off light excitation, the junctions show response speed as fast as 1 µs or better and noise equivalent powers comparable to commercial Si photomultipliers. Current-voltage measurements in dark and under illumination suggest that the devices consist of Schottky and semiconductor/semiconductor junctions both contributing to the fast and high responses observed.

A cross-functional nanostructured platform based on carbon nanotube-Si hybrid junctions: where photon harvesting meets gas sensing.

A combination of the functionalities of carbon nanotube (CNT)-Si hybrid heterojunctions is presented as a novel method to steer the efficiency of the photovoltaic (PV) cell based on these junctions, and to increase the selectivity and sensitivity of the chemiresistor gas sensor operated with the p-doped CNT layer. The electrical characteristics of the junctions have been tracked by exposing the devices to oxidizing (NO2) and reducing (NH3) molecules. It is shown that when used as PV cells, the cell efficiency can be reversibly steered by gas adsorption, providing a tool to selectively dope the p-type layer through molecular adsorption. Tracking of the current-voltage curve upon gas exposure also allowed to use these cells as gas sensors with an enhanced sensitivity as compared to that provided by a readout of the electrical signal from the CNT layer alone. In turn, the chemiresistive response was improved, both in terms of selectivity and sensitivity, by operating the system under illumination, as the photo-induced charges at the junction increase the p-doping of CNTs making them more sensitive to NH3 and less to NO2.

Growth Mechanisms of Inductively-Coupled Plasma Torch Synthesized Silicon Nanowires and their associated photoluminescence properties.

Ultra-thin Silicon Nanowires (SiNWs) were produced by means of an industrial inductively-coupled plasma (ICP) based process. Two families of SiNWs have been identified, namely long SiNWs (up to 2-3 micron in length) and shorter ones (~100 nm). SiNWs were found to consist of a Si core (with diameter as thin as 2 nm) and a silica shell, of which the thickness varies from 5 to 20 nm. By combining advanced transmission electron microscopy (TEM) techniques, we demonstrate that the growth of the long SiNWs occurred via the Oxide Assisted Growth (OAG) mechanism, while the Vapor Liquid Solid (VLS) mechanism is responsible for the growth of shorter ones. Energy filtered TEM analyses revealed, in some cases, the existence of chapelet-like Si nanocrystals embedded in an otherwise silica nanowire. Such nanostructures are believed to result from the exposure of some OAG SiNWs to high temperatures prevailing inside the reactor. Finally, the intense photoluminescence (PL) of these ICP-grown SiNWs in the 620-950 nm spectral range is a clear indication of the occurrence of quantum confinement. Such a PL emission is in accordance with the TEM results which revealed that the size of nanostructures are indeed below the exciton Bohr radius of silicon.

Steering the efficiency of carbon nanotube-silicon photovoltaic cells by acid vapor exposure: a real-time spectroscopic tracking.

Hybrid carbon nanotube-silicon (CNT-Si) junctions have been investigated by angle resolved photoemission spectroscopy (AR-XPS) with the aim to clarify the effects of a nonstoichiometric silicon oxide buried interface on the overall cell efficiency. A complex silicon oxide interface has been clearly identified and its origin and role in the heterojunction have been probed by exposing the cells to hydrofluoric (HF) and nitric (HNO3) acid. Real-time monitoring of the cell efficiencies during the steps following acid exposure (up to 1 week after etching) revealed a correlation between the thickness and chemical state of the oxide layer and the cell efficiencies. By matching the AR-XPS and Raman spectroscopy with the electrical response data it has been possible to discriminate the effects on the cell efficiency of the buried SiO(x) interface from those related to CNT acid doping. The overall cell behavior recorded for different thicknesses of the SiO(x) interface indicates that the buried oxide layer is likely acting as a passivating/inversion layer in a metal-insulator-semiconductor junction.

A three-dimensional carbon nanotube network for water treatment.

The bulk synthesis of freestanding carbon nanotube (CNT) frameworks is developed through a sulfur-addition strategy during an ambient-pressure chemical vapour deposition process, with ferrocene used as the catalyst precursor. This approach enhances the CNTs' length and contorted morphology, which are the key features leading to the formation of the synthesized porous networks. We demonstrate that such a three-dimensional structure selectively uptakes from water a mass of toxic organic solvent (i.e. o-dichlorobenzene) about 3.5 times higher than that absorbed by individual CNTs. In addition, owing to the presence of highly defective nanostructures constituting them, our samples exhibit an oil-absorption capacity higher than that reported in the literature for similar CNT sponges.

Electronic and optoelectronic nano-devices based on carbon nanotubes.

The discovery and understanding of nanoscale phenomena and the assembly of nanostructures into different devices are among the most promising fields of material science research. In this scenario, carbon nanostructures have a special role since, in having only one chemical element, they allow physical properties to be calculated with high precision for comparison with experiment. Carbon nanostructures, and carbon nanotubes (CNTs) in particular, have such remarkable electronic and structural properties that they are used as active building blocks for a large variety of nanoscale devices. We review here the latest advances in research involving carbon nanotubes as active components in electronic and optoelectronic nano-devices. Opportunities for future research are also identified.

Enhanced UV photoresponse of KrF-laser-synthesized single-wall carbon nanotubes/n-silicon hybrid photovoltaic devices.

We report on the KrF-laser ablation synthesis, purification and photocurrent generation properties of single-wall carbon nanotubes (SWCNTs). The thermally purified SWCNTs are integrated into hybrid photovoltaic (PV) devices by spin-coating them onto n-Si substrates. These novel SWCNTs/n-Si hybrid devices are shown to generate significant photocurrent (PC) over the entire 250-1050 nm light spectrum with external quantum efficiencies (EQE) reaching up to ~23%. Our SWCNTs/n-Si hybrid devices are not only photoactive in the traditional spectral range of Si solar cells, but generate also significant PC in the UV domain (below 400 nm). This wider spectral response is believed to be the result of PC generation from both the SWCNTs themselves and the tremendous number of local p-n junctions created at the nanotubes/Si interface. To assess the prevalence of these two contributions, the EQE spectra and J-V characteristics of these hybrid devices were investigated in both planar and top-down configurations, as a function of SWCNTs' film thickness. A sizable increase in EQE in the near UV with respect to the silicon is observed in both configurations, with a more pronounced UV photoresponse in the planar mode, confirming thereby the role of SWCNTs in the photogeneration process. The PC generation is found to reach its maximum for an optimal the SWCNT film thickness, which is shown to correspond to the best trade-off between lowest electrical resistance and highest optical transparency. Finally, by analyzing the J-V characteristics of our SWCNTs/n-Si devices with an equivalent circuit model, we were able to point out the contribution of the various electrical components involved in the photogeneration process. The SWCNTs-based devices demonstrated here open up the prospect for their use in highly effective photovoltaics and/or UV-light sensors.

Ferromagnetic Mn-doped Si0.3Ge0.7 nanodots self-assembled on Si(100).

Densely packed epitaxial Mn-doped Si(0.3)Ge(0.7) nanodots self-assembled on Si(100) have been obtained. Their structural properties were studied using reflection high-energy electron diffraction, energy dispersive x-ray diffraction, atomic force microscopy, extended x-ray absorption fine structure measurements and high-resolution transmission electron microscopy. Mn(5)Ge(1)Si(2) crystallites embedded in Si(0.3)Ge(0.7) were found. They exhibit a ferromagnetic behaviour with a Curie temperature of about 225 K.

Playing with peptides: how to build a supramolecular peptide nanostructure by exploiting helix···helix macrodipole interactions.

A novel method to build bicomponent peptide self-assembled monolayers (SAMs) has been developed, by exploiting helix···helix macrodipole interactions. In this work, a peptide-based self-assembled monolayer composed of two helical peptides was immobilized on a gold surface. Specifically, a pyrene-containing octapeptide, devoid of any sulfur atom (A8Pyr), and a hexapeptide, functionalized at the N-terminus with (S,R) lipoic acid, for binding to gold substrates (SSA4WA) via a Au-S linkage, have been employed. Both peptides investigated attain a helical structure, because they are almost exclusively formed by strongly folding inducer C(α)-tetrasubstituted α-amino acids. We demonstrate that the two peptides generate a stable supramolecular nanostructure (a densely packed bicomponent peptide monolayer), where A8Pyr is incorporated into the SSA4WA palisade by exploiting helix···helix macrodipole interactions. The presence of both peptides on the gold surface was investigated by spectroscopic and electrochemical techniques, while the morphology of the monolayer was analyzed by ultra high-vacuum scanning tunnelling microscopy. The composition of the bicomponent SAM on the surface was studied by a combination of electrochemical and spectroscopic techniques. In particular, the amount of Au-S linkages from the sulfur-containing peptides was quantified from reductive desorption of the peptide-based SAM, while the amount of A8Pyr was estimated by fluorescence spectroscopy. The antiparallel orientation of the A8Pyr and SSA4WA peptide chains minimizes the interaction energy between the helix dipoles, suggesting that this kind of electrostatic phenomenon is the driving force that stabilizes the bicomponent SAM.

Influence of Cu nanoparticle size on the photo-electrochemical response from Cu-multiwall carbon nanotube composites.

We show that Cu metal nanoparticle-multiwall carbon nanotube (MWCNT) assemblies can act as a new hybrid photoactive layer in photo-electrochemical devices. The carbon nanotube (CNT) composites were formed by a controlled thermal deposition of copper which produced crystalline metal nanoparticles localized on the carbon tube outer walls. The photoresponse evaluated in terms of IPCE (incident photon-to-charge carrier generation efficiency) varied for different sized-Cu-MWCNT samples across all the visible and near ultraviolet photon energy range with respect to the response of bare MWCNTs. In the case of 0.2 nm Cu nominal thickness, the IPCE increased, reaching 15%, a value 2.5 times higher than that measured for bare MWCNTs. As the Cu nominal coverage thickened, the IPCE started to decrease and become totally ineffective after 1 nm deposited Cu. The IPCE increase found was interpreted as being the result of a remarkable charge transfer between the Cu metal nanoparticles and the CNTs due to the formation of a strong ionic bond at their interface. The results obtained prove that the metal nanoparticle-CNT composites have optical, electrical and structural properties that can be applied in a variety of nanoscale architectures for novel photo-electrochemical devices.

Photovoltaic response of carbon nanotube-silicon heterojunctions: effect of nanotube film thickness and number of walls.

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.

Tuning photoresponse through size control of Cu nanoparticles deposited on multi wall carbon nanotubes.

In this paper we illustrate a simple method for the production of multiwall carbon nanotubes thin films decorated with copper metal nanoparticles. The structural information obtained from the transmission electron microscopy study performed on samples differing in the quantity of deposited Copper was linked to the opto-electronic properties evaluated with photo-electrochemical measurements. The photo-response evaluated in terms of incident photon-to-charge carrier generation efficiency varied for different sized-Cu-multiwall carbon nanotubes samples across all the visible and near-ultraviolet photon energy range with respect to the response of bare carbon tubes. The photo-response from the sample covered with of 0.5 nm Cu nominal thickness, reached 10.2%, a value 2 times higher than that measured for bare carbon tubes of 5.9%. While this value decreased to 2.8% when the Cu nominal coverage thickened up to 3 nm. The increase in the photo-response found was interpreted as being the result of a remarkable charge transfer between the Cu metal nanoparticles and the carbon atoms in the tube due to the formation of a strong ionic bond at their interface. The results obtained prove that the metal nanoparticle-carbon nanotube composites have optical, electrical and structural properties that can be applied in a variety of nanoscale architectures for novel photo-electrochemical devices.