Paola Castrucci

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.

Experimental imaging of silicon nanotubes

Transmission electron microscopy (TEM), electron energy loss near edge structures (EELNES) and scanning tunneling microscopy (STM) were used to distinguish silicon nanotubes (SiNT) among the reaction products of a gas phase condensation synthesis. TEM images exhibit the tubular nature with a well-defined wall. The EELNES spectra performed on each single nanotube show that they are constituted by nonoxidized silicon atoms. STM images show that they have diameter ranging from 2 to 35 nm, have an atomic arrangement compatible with a puckered structure and different chiralities. Moreover, the I-V curves showed that SiNT can be semiconducting as well as metallic in character.

Large photocurrent generation in multiwall carbon nanotubes

The authors demonstrate the ability of multiwall carbon nanotubes to generate photocurrents in the near ultraviolet and visible spectral ranges using electrochemical photocurrent measurements. The photogenerated current depends on the excitation wavelength similar to that for single wall carbon nanotubes. Its intensity and modulation can be related to the carbon nanotubes morphology. The maximum photon-to-current conversion efficiency is approximately 7%, about 50 times higher than that reported for single wall carbon nanotubes. This result is of particular relevance for photovoltaic nanodevices and solar energy conversion applications.

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.

Effect of coiling on the electronic properties along single-wall carbon nanotubes

Straight and coiled single-wall carbon nanotubes (SWCNTs) synthesized by laser vaporization were dispersed on highly oriented pyrolitic graphite. Their morphology and electrical properties were investigated by scanning tunneling microscopy (STM). STM images revealed that the SWCNTs (either straight or coiled) often self-organize into bundles of two or more tubes and are rarely found alone. The conductance measured along a periodically coiled CNT was found to increase at locations where the CNT is squeezed, while it decreases significantly in unsqueezed regions characterized by an unperturbed hexagonal network. This provides experimental evidence of significant conductance modulation along a one-dimensional system on the nanometer scale.

Carbon nanotube semitransparent electrodes for amorphous silicon based photovoltaic devices

Different amounts of single wall carbon nanotubes (SWCNTs) have been sprayed on amorphous silicon substrates to form Schottky barrier solar cells. The measured external quantum efficiency showed a spectral behavior depending on the SWCNT network optical transparency, presenting a maximum up to 35% at a wavelength of about 460 nm. Ultrathin network of SWCNTs acts as semitransparent electrode and forms Schottky barrier with amorphous silicon, enabling new generation low cost amorphous silicon based solar cells. Numerical simulations show a poor efficiency of SWCNT contacts in collecting holes suggesting that improvement in contact quality is needed to further improve solar cell efficiency.

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.

Photocurrent generation in random networks of multiwall-carbon-nanotubes grown by an “all-laser” process

We report photocurrent generation in entangled networks of multiwall-carbon nanotubes (MWCNTs) grown on TiN/Si substrates by an all-laser process. By integrating these MWCNTs into planar devices, we demonstrate that they generate photocurrent over all the visible and near-ultraviolet range, with maximum efficiency around 420 nm. Photocurrent is obtained even at zero applied voltage, pointing to a true photovoltaic (PV) effect. The extracted photocurrent as a function of applied voltage exhibits nonlinear behavior for voltages ≥2 V, suggesting that the devices do not behave as pure photoresistances. Other mechanisms (e.g., Schottky barriers imbalance) are invoked to describe current flow in these PV devices.