The multifunctional properties of carbon nanotubes (CNTs) make them a powerful platform for unprecedented innovations in a variety of practical applications. As a result of the surging growth of nanotechnology, nanotubes present a potential problem as an environmental pollutant, and as such, an efficient method for their rapid detection must be established. Here, we propose a novel type of ionic sensor complex for detecting CNTs – an organic dye that responds sensitively and selectively to CNTs with a photoluminescent signal. The complexes are formed through Coulomb attractions between dye molecules with uncompensated charges and CNTs covered with an ionic surfactant in water. We demonstrate that the photoluminescent excitation of the dye can be transferred to the nanotubes, resulting in selective and strong amplification (up to a factor of 6) of the light emission from the excitonic levels of CNTs in the near-infrared spectral range, as experimentally observed via excitation-emission photoluminescence (PL) mapping. The chirality of the nanotubes and the type of ionic surfactant used to disperse the nanotubes both strongly affect the amplification; thus, the complexation provides sensing selectivity towards specific CNTs. Additionally, neither similar uncharged dyes nor CNTs covered with neutral surfactant form such complexes. As model organic molecules, we use a family of polymethine dyes with an easily tailorable molecular structure and, consequently, tunable absorbance and PL characteristics. This provides us with a versatile tool for the controllable photonic and electronic engineering of an efficient probe for CNT detection.

An excimer in J-aggregates has been often considered as a self-trapped exciton originating from the free exciton excited on the same aggregate and relaxed through interaction with vibronic modes. Here we show that other types of excimers due to intermolecular off-diagonal interactions can be observed in J-aggregates of thiamonomethinecyanine dyes. These excimers arise owing to free excitons too, but they possess a longer formation time of more than 100 ps, indicating migration of free excitons to the excimer formation site, where they interact with a guest species in the ground state. Formation of the excimers occurs in solutions as a power law of concentration with an exponent of 1.5, showing that an excited aggregate should be twice longer than a ground-state guest species, consistent with the exciton coherence length of four molecules versus one dimer, respectively. Unlike the self-trapped exciton, lower temperatures lead to significant suppression of the observed excimer emission.

Photoluminescence, electronic absorption, and pH studies of a poly(ethylene-3,4-dioxythiophene):poly(styrenesulfonic acid) (PEDOT:PSS) dispersion as a function of the PEDOT:PSS concentration are shown to provide a better understanding of the effect of PSS on the intramolecular conductivity of PEDOT chains. Particularly, concentration changes of PEDOT:PSS were found to be accompanied with different extents of dissociation of protons in the solution and different charge states of PSS chains, respectively, which affect the electrostatic interaction between PSS and PEDOT and intramolecular conductivity in the PEDOT backbone.

We report significant improvements in the structure and electronic properties of a poly(3-alkylthiophene) representative, namely poly(3-methylthiophene) (P3MT), when it is synthesized in the presence of submicron electroactive poly(vinylidene fluoride) (PVDF) particles. The applied template oxidative synthesis leads to the formation of the PVDF/P3MT composite consisting of core-shell particles. The shells are constituted with a monolayer of 20-40 nm nanoparticles of the doped P3MT (P3MT-Cl) precipitated at the surface of the spherical PVDF cores. This morphology differs strongly from the hierarchical one of the neat P3MT synthesized without PVDF particles. In the latter case, 20-60 nm P3MT nanoparticles form ∼200 nm aggregates, which, in turn, are arranged in a few micrometer agglomerates. Furthermore, we demonstrate that compared to the neat polymer, doped P3MT in the shells of the composite is characterized with higher effective conjugation length, regioregularity of the molecular structure, improved intrachain packing order and lower bipolaron/polaron ratio. These features of the PVDF/P3MT composite strongly suggest applicability of this material in various electronic devices. As a proof of concept, we report on an improved sensing performance of the PVDF/P3MT-Cl composite compared with the neat P3MT-Cl in detection of several volatile organic compounds known as markers for some diseases and toxic substances. We have discovered that the maximal improvement in the sensor response magnitude corresponds to the case when the values of the analyte electronegativity and polythiophene work function are close. We associate this behavior with a higher surface dipole component of the work function of the PVDF/P3MT-Cl composite compared to that of the neat conducting polymer.