Solubilizing and purifying carbon nanotubes remains one of the foremost technological hurdles in their investigation and application. We report a dramatic improvement in the preparation of single-walled carbon nanotube solutions based on the ability of specific aromatic polymers to efficiently disperse certain nanotube species with a high degree of selectivity. Evidence of this is provided by optical absorbance and photoluminescence excitation spectra, which show suspensions corresponding to up to approximately 60% relative concentration of a single species of isolated nanotubes with fluorescence quantum yields of up to 1.5%. Different polymers show the ability to discriminate between nanotube species in terms of either diameter or chiral angle. Modelling suggests that rigid-backbone polymers form ordered molecular structures surrounding the nanotubes with n-fold symmetry determined by the tube diameter.
Combinations of different aromatic polymers and organic solvents have been studied as dispersing agents for preparing single-walled carbon nanotubes solutions, using optical absorbance, photoluminescence-excitation mapping, computer modeling, and electron microscopic imaging to characterize the solutions. Both the polymer structure and solvent used strongly influence the dispersion of the nanotubes, leading in some cases to very high selectivity in terms of diameter and chiral angle. The highest selectivities are observed using toluene with the rigid polymers PFO-BT and PFO to suspend isolated nanotubes. The specific nanotube species selected are also dependent on the solvent used and can be adjusted by the use of THF or xylene. Where the structure has more flexible conformations, the polymers are shown to be less selective but show an enhanced overall solubilization of nanotube material. When chloroform is used as the solvent, there is a large increase in the overall solubilization, but the nanotubes are suspended as bundles rather than as isolated tubes which leads to a quenching of their photoluminescence.
We report a study of the electronic properties of the heterojunction between regioregular poly(3-hexylthiophene) (rrP3HT) and single-walled carbon nanotubes (SWNTs). Comparison of the spectroscopic data of nanotube dispersions in a range of polymers indicates significant changes in the nature of the observed SWNT excitons only in combination with rrP3HT. A detailed analysis concludes that a type II heterojunction between rrP3HT and small diameter s-SWNTs is formed, making these particular nanohybrids a promising material for organic photovoltaics.
We report on the synthesis and spectroscopic study of a novel highly ordered nanohybrid structure consisting of a single-walled carbon nanotube (SWNT) coated with highly crystalline regio-regular poly(3-hexylthiophene) (rrP3HT) and discuss the applicability of the nanohybrids in organic photovoltaics. The use of a solvent extraction technique allows the nanohybrids to be produced with a high yield and high purity. We find evidence that the crystallinity of rrP3HT is enhanced in the presence of SWNTs, which introduces a reduced optical band gap and increased carrier mobility in the polymer. Study of the photoluminescence excitation spectra of the SWNTs reveals an efficient energy transfer of excitons created on the rrP3HT to the SWNTs. This energy transfer is expected to limit our ability to use the nanohybrids as a charge separating interface and can therefore explain the low efficiency of P3HT-SWNT solar cells produced to date. In addition, careful consideration of the energy transfer is necessary when attempting to improve state of the art polymer-fullerene photovoltaic devices with SWNTs in order to make use of their high charge carrier mobilities and increased rrP3HT crystallinity.
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