Antonio Setaro

Preserving π-conjugation in covalently functionalized carbon nanotubes for ptoelectronic applications

Covalent functionalization tailors carbon nanotubes for a wide range of applications in varying environments. Its strength and stability of attachment come at the price of degrading the carbon nanotubes sp2 network and destroying the tubes electronic and optoelectronic features. Here we present a non-destructive, covalent, gram-scale functionalization of single-walled carbon nanotubes by a new [2+1] cycloaddition. The reaction rebuilds the extended π-network, thereby retaining the outstanding quantum optoelectronic properties of carbon nanotubes, including bright light emission at high degree of functionalization (1 group per 25 carbon atoms). The conjugation method described here opens the way for advanced tailoring nanotubes as demonstrated for light-triggered reversible doping through photochromic molecular switches and nanoplasmonic gold-nanotube hybrids with enhanced infrared light emission.

Polyglycerol-derived amphiphiles for the solubilization of single-walled carbon nanotubes in water: a structure-property study.

A series of nonionic amphiphiles derived from polyglycerol dendrons were studied for their ability to solubilize and isolate single-walled carbon nanotubes. The amphiphiles possessed differently sized polar head groups, hydrophobic tail units, and various aromatic and non-aromatic groups between the head and tail groups. Absorbance analysis revealed that amphiphiles with anchor groups derived from pyrene were far inferior to those that possessed simple linear aliphatic tail groups. Absorbance and near-infrared fluorescence analyses revealed a weak dependence on the dendron size of the head group, but a strong positive trend in suspended nanotube density and fluorescence intensity for amphiphiles with longer tail units. Variations in the moieties linking the head and tail groups led to a range of effects on the suspensions, with linkers imparting flexibility and a bent shape that gave improved performance overall. This was illustrated most dramatically by a pair of benzamide-containing amphiphiles, the para isomer of which showed evidence in the fluorescence data of increased nanotube aggregate formation when compared with the meta isomer. In addition, statistical AFM was used to illustrate more directly the microscopic differences between amphiphiles that were effective at nanotube bundle disruption and those that were not.

Nanoplasmonic colloidal suspensions for the enhancement of the luminescent emission from single-walled carbon nanotubes

Aiming to enhance the luminescence yield of carbon nanotubes, we introduce a new class of hybrid nanoplasmonic colloidal systems (π-hybrids). Nanotubes dispersed in gold nanorod colloidal suspensions yield hybrid structures exhibiting enhanced luminescence up to a factor of 20. The novelty of the proposed enhancement mechanism relies on including metal proximity effects in addition to its localized surface plasmons. This simple, robust and flexible technique enhances the luminescence of nanotubes with chiralities whose enhancement has never reported before, for example the (8,4) tube.

Carbon nanotubes as substrates for molecular spiropyran-based switches

We present a joint theory-experiment study investigating the excitonic absorption of spiropyran-functionalized carbon nanotubes. The functionalization is promising for engineering switches on a molecular level, since spiropyrans can be reversibly switched between two different conformations, inducing a distinguishable and measurable change of optical transition energies in the substrate nanotube. Here, we address the question of whether an optical read-out of such a molecular switch is possible. Combining density matrix and density functional theory, we first calculate the excitonic absorption of pristine and functionalized nanotubes. Depending on the switching state of the attached molecule, we observe a red-shift of transition energies by about 15 meV due to the coupling of excitons with the molecular dipole moment. Then we perform experiments measuring the absorption spectrum of functionalized carbon nanotubes for both conformations of the spiropyran molecule. We find good qualitative agreement between the theoretically predicted and experimentally measured red-shift, confirming the possibility for an optical read-out of the nanotube-based molecular switch.

Excitation characteristics of different energy transfer in nanotube-perylene complexes

We report the properties of perylene-nanotube complexes that form efficient energy transfer systems. Most perylene-derivatives yield similar ratios between transfer and direct luminescence (0.66 ± 0.04). The photoluminescence spectra of the free compounds and the transfer complex are similar indicating that perylene and nanotubes act as separate systems. A further increase in interaction yields 40% higher transfer rates and luminescence excitation spectra that indicate a change in stacking of the perylene on the nanotube wall. All measurements are consistent with a transfer mechanism based on a dipole-dipole interaction at a distance much smaller than the Forster radius.

Relaxation lifetimes of plasmonically enhanced hybrid gold-carbon nanotubes systems

Recently, we introduced a novel hybridization route for carbon nanotubes using gold nanoparticles, whose close proximity neatly enhances their radiative emission. Here we investigate the mechanisms behind the enhancement by monitoring the de-excitation dynamics of our π-hybrids through two-color pump-probe time-resolved spectroscopy. The de-excitation process reveals a fast component and a slow component. We find that the presence of gold prominently affects the fast processes, indicating a stronger influence of the gold nanoparticle on the intra-band non-radiative relaxation than on the inter-band recombination of the single-walled carbon nanotube. By evaluating the de-excitation times, we estimate the balance between near-field pumping and the faster metal-induced de-excitation contributions, proving the enhanced pumping to be the leading mechanism.