"Awakening" of the S2 Emission of Tricarbocyanine Dyes Stimulated by Interaction with Carbon Quantum Dots.

Anti-Kasha emission (i.e., the emission from Sn (n > 1) excited levels) of infrared chromophores which possess intensive absorption and S1 emission in the near-infrared region, but which are spectrally silent in the visible, is a challenging task for relevant applications such as energy conversion, bioimaging, sensitization of solar cells, optical sensors, and so on. Here we demonstrate a dual emission of near-infrared tricarbocyanine dyes with a bright green S2 fluorescence, whose quantum yield increases by 2-4 times together with a strong enhancement of the spontaneous rate of S2 fluorescence, whereas the quantum yield of S1 emission decreases by 2-7 times, respectively, as a result of immobilization of the dye molecule via interaction with carbon quantum dots. The enhanced immobilization-induced S2 emission is shown to occur because of planarization of the molecule and freezing its rotational degrees of freedom as indicated by suppression of the dye hot-band absorption-assisted anti-Stokes S1 emission.

Dynamics of Excitons in Conjugated Molecules and Organic Semiconductor Systems.

The exciton, an excited electron-hole pair bound by Coulomb attraction, plays a key role in photophysics of organic molecules and drives practically important phenomena such as photoinduced mechanical motions of a molecule, photochemical conversions, energy transfer, generation of free charge carriers, etc. Its behavior in extended π-conjugated molecules and disordered organic films is very different and very rich compared with exciton behavior in inorganic semiconductor crystals. Due to the high degree of variability of organic systems themselves, the exciton not only exerts changes on molecules that carry it but undergoes its own changes during all phases of its lifetime, that is, birth, conversion and transport, and decay. The goal of this review is to give a systematic and comprehensive view on exciton behavior in π-conjugated molecules and molecular assemblies at all phases of exciton evolution with emphasis on rates typical for this dynamic picture and various consequences of the above dynamics. To uncover the rich variety of exciton behavior, details of exciton formation, exciton transport, exciton energy conversion, direct and reverse intersystem crossing, and radiative and nonradiative decay are considered in different systems, where these processes lead to or are influenced by static and dynamic disorder, charge distribution symmetry breaking, photoinduced reactions, electron and proton transfer, structural rearrangements, exciton coupling with vibrations and intermediate particles, and exciton dissociation and annihilation as well.

Reversible Charge Transfer with Single-Walled Carbon Nanotubes Upon Harvesting the Low Energy Part of the Solar Spectrum.

Here, the ability of a novel near-infrared dye to noncovalently self-assemble onto the surface of single-walled carbon nanotubes (SWCNTs) driven by charge-transfer interactions is demonstrated. Steady-state, Raman, and transient absorption spectroscopies corroborate the electron donating character of the near-infrared dye when combined with SWCNTs, in the form of fluorescence quenching of the excited state of the dye, n-doping of SWCNTs, and reversible charge transfer, respectively. Formation of the one-electron oxidized dye as a result of interactions with SWCNTs is supported by spectroelectrochemical measurements. The ultrafast electronic process in the near-infrared dye, once immobilized onto SWCNTs, starts with the formation of excited states, which decay to the ground state via the intermediate population of a fully charge-separated state, with characteristic time constants for the charge separation of 1.5 ps and charge recombination of 25 ps, as derived from the multiwavelength global analysis. Of great relevance is the fact that charge-transfer occurs from the hot excited state of the near-infrared dye to SWCNTs.

Excimer Emission in J-Aggregates.

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.

Effect of Confinement on Photophysical Properties of P3HT Chains in PMMA Matrix.

The influence of arrangement of poly(3-hexylthiophene) (P3HT) chains embedded into poly(methyl methacrylate) (PMMA) matrix on photophysical properties, such as electronic absorption spectrum, band gap, and photoluminescence quantum yield, of the formed P3HT aggregates have been studied. It has been found that variation of P3HT fraction in PMMA matrix from 25 to 2 wt% is accompanied with the increasing quantum yield of photoluminescence, red shift of the band gap, and structural change of P3HT crystallites. The above changes are accompanied with disruption of the continuous network of P3HT fraction into smaller P3HT particles with size ranged from several microns to several tens of nanometers. The results are interpreted in terms of the changing intermolecular packing and reduced intramolecular torsional disorder. It is discussed that the most contribution to the above changes comes from P3HT molecules at the interface of P3HT cluster and PMMA environment.

Hybrid solar cell on a carbon fiber.

In this work, a method to assemble nanoscale hybrid solar cells in the form of a brush of radially oriented CdS nanowire crystals around a single carbon fiber is demonstrated for the first time. A solar cell was assembled on a carbon fiber with a diameter of ~5-10 µm which served as a core electrode; inorganic CdS nanowire crystals and organic dye or polymer layers were successively deposited on the carbon fiber as active components resulting in a core-shell photovoltaic structure. Polymer, dye-sensitized, and inverted solar cells have been prepared and compared with their analogues made on the flat indium-tin oxide electrode.

Light-induced self-assembly and decay of J aggregates of thiamonomethinecyanine dyes.

Formation of J aggregates, that is, one-dimensional supramolecular self-organizations in which the transition moments of individual molecules are aligned parallel to the line joining their centers through a "head-to-tail" arrangement, normally proceed via electrostatic interactions between oppositely charged molecular groups; this is facilitated by an electrolyte medium. Here, we show that J aggregates of thiamonomethinecyanine dyes in a solution can be assembled from dye dimers by illuminating the solution with light of the appropriate wavelength to induce excitation of the dye dimers. The reverse process is also demonstrated by application of light of the correct wavelength to induce excitation of the J aggregates. Our results indicate that spontaneous J aggregation in the dark and formation of J aggregates through illumination proceed through different mechanisms; the former resulting in an increase in the number of the aggregates and the latter in an increase in the size of the aggregates.

Evidence of the controlled interaction between PEDOT and PSS in the PEDOT:PSS complex via concentration changes of the complex solution.

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.

Confinement of polyaniline chains in capillary layers: an ordering effect of the uniaxially aligned surfaces.

An ordering effect of uniaxially aligned poly(tetrafluoroethylene) (PTFE) substrates prepared by rubbing on polyaniline (PANI) molecules at the interfaces of PTFE/PANI film and PTFE/PANI solution has been investigated using electronic absorption spectroscopy. It was observed slight dichroism in electronic spectra from only very thin (thickness approximately 20 nm and less) PANI films as well as from PANI solutions of capillary thickness (10 to 30 microm) confined by oriented PTFE surfaces. The ordering effect is discussed in terms of a hydrodynamic flow arising upon sample formation and steric factors at the PTFE surface, which cause uniaxial deformation of the polymer coil on the rubbed PTFE surface.

Confinement of Polyaniline Chains in Thin Layers of the Polymer Solution.

Electronic absorption spectra of polyaniline (PANI) solutions in a transparent cell were observed to change as the cell gap was reduced to approximately 10 µm. Although the cell gap size was wide enough, at least two orders of magnitude larger than the polymer coils in the solution, the observed changes were explained by self-confinement of polymer molecules at the liquid/solid interface as a result of their intense adsorption and depletion of the relatively small solution volume, respectively. It was shown that the cell material affects electronic spectra of confined polymer solutions. Copyright 2001 Academic Press.