Modeling of the infrared vibrational dynamics of oligothiophenes embedded in carbon nanotubes

The rise of efficient extraction techniques triggered a renewal of interest in semiconducting carbon nanotube (s-SWNT) research. It represents a great interest for optoelectronics, with outstanding properties in field-effect transistor, and s-SWNT ability to efficiently emit light in the near-IR range. In particular, the hybrid system polyfluorene (PFO) wrapped s‑SWNT (s-SWNT@PFO) display strong photoluminescence, and could be coupled with photonic devices such as microring resonators to control photoluminescence linewidth and enhance photoluminescence intensity.The main challenge for using s-SWNT@PFO in optoelectronics lies in the difficulty to establish good electrical contact with a PFO embedded carbon nanotube, and existing studies only focused on optical pumping of carbon nanotube networks, without addressing issues of electrical driving.We propose to investigate these issues using suspended s-SWNT@PFO networks. The network formation process allow to control nanotube density, while the amount of remaining metallic nanotube in the network could be adjusted at the extraction phase. A selective annealing process under low pressure is used to tune PFO wrapping around the nanotubes. The resulting s-SWNT@PFO networks are then probed by AFM, Raman spectroscopy, absorption, photoluminescence and electrical experiments.

Infrared response on a carbon nanotube is weak because this homonuclear allotrope of carbon does not bear permanent dipoles. Here, we report the discovery of an exaltation of the infrared absorption response in single-walled carbon nanotubes from dye molecule interactions. A study performed on dimethylquaterthiophene confined into the hollow core of single-walled carbon nanotubes or π-stacked at the outer surface of the latter leads to a symmetry breaking, allowing us to probe interactions between both subsystems. The nature of these interactions is discussed taking into account the tube diameter. This new phenomenon opens a new route to detect weak vibrations thanks to a confinement effect.

Opto-electronic properties of single-walled carbon nanotubes can be significantly modified by chromophore confinement into their hollow core. This study deals with quaterthiophene derivatives encapsulated into nanotubes displaying different diameter distributions. We report a significant electron transfer from the confined molecules to the nanotubes in our hybrid systems, evidenced by photoluminescence and Raman investigations. This charge transfer leads to an important enhancement of the photoluminescence intensity by a factor of nearly five depending on the tube diameter. Energy shifts observed on both absorption and emission on the hybrid system also depend on the nanotube diameters and are interpreted in terms of local structure of the confined molecules. The Raman G-band of hybrid systems exhibits a drop in intensity and significant shifts whose magnitude and direction strongly depend on the nanotube diameter. These behaviors are consistent with a weak electron transfer from the molecule to the tube, in good agreement with the PL analysis. In addition, close to the molecule resonance, the magnitude of the G-band shifts are modified and the intensity loss is amplified, strongly suggesting a photo-induced electron transfer. Finally, the Breit-Wigner-Fano lineshape (characteristic of electron-phonon coupling) of the Raman G-band is strongly reduced for defective metallic nanotubes. After molecule functionalization, this peculiar profile is recovered, suggesting a back donation of electrons to the nanotube. Thus, confinement species into nanotubes allow moving the Fermi level and consequently to monitor their opto-electronic properties.

Opto-electronic properties of single-walled carbon nanotubes can be significantly modified by chromophore confinement into their hollow core. For instance, charge transfers are evidenced from Raman data analysis. First, by exciting nanotubes far from the optical absorption of the molecule, the Raman G-band signal exhibits a weak but significant up or downshift depending on the nanotube diameters. This behavior is consistent with a permanent electron transfer to the nanotube in the framework of the renormalization process 1. In addition, close to the molecule resonance, the magnitude of the G-band shift is enhanced for small diameter tubes, evidencing a photo-induced electron transfer. Finally, the Breit-Wigner-Fano lineshape (characteristic of electron-phonon coupling) of the Raman G-band can be strongly reduced for defective metallic nanotubes. After molecule functionalization, this peculiar profile is recovered, suggesting a back donation of electrons to the nanotube. Photoluminescence properties of semiconducting nanotubes are also significantly modified by chromophore confinement. The nanotube emission intensity is amplified after encapsulation. This exaltation depends on the nanotube diameter, and can be related to diameters exactly fitting the molecule size. The origin of the photoluminescence enhancement will be discussed.

Wet acid oxidation treatment methods have been widely reported as an effective method to purify and oxidize the surface of industrial multi-walled carbon nanotubes (MWCNT). This work examines the use of a concentrated HNO3/H2SO4 mixture in an attempt to optimize the purification procedure of industrial MWCNT with diameter distribution statistics. It is shown that acid treatments of several hours are enough to purify the nanotubes. The electrical and thermal conductivities of epoxy composites containing 0.05-0.25 wt. % of acid-treated MWCNT has been studied. The electrical conductivity of the composites decreases by more than three orders, whereas the thermal conductivity of the same specimen increases very modestly as a function of the filler content.

Photo-active pi-conjugated molecules (quaterthiophene and phthalocyanine) are either encapsulated into the hollow core of single-walled carbon nanotubes or non-covalently stacked at their outer surface in order to elaborate hybrid nano-systems with new physical properties, providing practical routes to fit different requirements for potential applications. In this study, we are interested in the relationship between the structure and the opto-electronic properties. The structural properties are investigated mainly by x-ray diffraction and/or Transmission Electron Microscopy and Raman spectroscopy. We evidence that the supramolecular organizations of confined quaterthiophenes depend on the nanocontainer size whereas phthalocyanine encapsulation leads the formation of a 1D-phase for which the angle between the molecule ring and the nanotube axis is close to 32°. Confined phthalocyanine molecules display Raman spectra hardly altered with respect to the bulk phase, suggesting a rather weak interaction with the tubes. In contrast, the vibrational properties of the molecules stacked at the outer surface of tubes display important modifications. We assume a significant curvature of the phthalocyanine induced by the interaction with the tube walls and a change of the central atom position within the molecular ring, in good agreement with our DFT calculations.