Detection of Ultralow Concentrations of Non-emissive Conjugated Polymer Aggregates via Fluorescence Correlation Spectroscopy.

The aggregation of conjugated polymers in common organic solvents is investigated using fluorescence correlation spectroscopy (FCS), burst analysis, and microscopy. Poly(3-hexylthiophene) and poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] are both shown to form weakly bonded non-emissive aggregates in toluene that persist even at picomolar concentrations. These aggregates decrease the bulk emission intensity in solution but do not affect the fluorescence spectra or lifetimes, consistent with a static quenching mechanism. Passing the solutions through a syringe filter causes an increase in the number of emitters as measured by FCS, indicating that this process dissociates the aggregates. Films cast from solutions that have been filtered are more uniform and significantly more emissive than those made from unfiltered solutions. These results show that FCS is a highly sensitive probe of non-emissive aggregates in solution that have a deleterious effect on the emission properties and overall quality of spin-cast thin films, even at sub-nanomolar concentrations.

Exciton-Exciton Annihilation as a Probe of Interchain Interactions in PPV-Oligomer Aggregates.

One measure of exciton mobility in an aggregate is the efficiency of exciton-exciton annihilation (EEA). Both exciton mobilities and EEA are enhanced for aggregate morphologies in which the distances between chromophores and their relative orientations are favorable for Förster energy transfer. Here this principle is applied to gauge the strength of interchain interactions in aggregates of two substituted PPV oligomers of 7 (OPPV7) and 13 (OPPV13) phenylene rings. These are models of the semiconducting conjugated polymer MEH-PPV. The aggregates were formed by adding a poor solvent (methanol or water) to the oligomers dissolved in a good solvent. Aggregates formed from the longer-chain oligomer and/or by addition of the more polar solvent showed the largest contribution of EEA in their emission decay dynamics. This was found to correlate with the degree to which the steady-state emission spectrum of the monomer is altered by aggregation. The wavelength dependence of the EEA signal was also shown to be useful in differentiating emission features due to monomeric and aggregated chains when their spectra overlap significantly.

The effects of side-chain-induced disorder on the emission spectra and quantum yields of oligothiophene nanoaggregates: a combined experimental and MD-TDDFT study.

Oligomeric thiophenes are commonly used components in organic electronics and solar cells. These molecules stack and/or aggregate readily under the processing conditions used to form thin films for these applications, significantly altering their optical and charge-transport properties. To determine how these effects depend on the substitution pattern of the thiophene main chains, nanoaggregates of three sexithiophene oligomers having different alkyl substitution patterns were formed using solvent-poisoning techniques and studied using steady-state and time-resolved emission spectroscopy. The results indicate the substantial role played by the side-chain substituents in determining the emissive properties of these species. Both the measured spectral changes and their dependence on substitution are well-modeled by combined quantum chemistry and molecular dynamics simulations. The simulations connect the side-chain-induced disorder, which determines the favorable chain-packing configurations within the aggregates, with their measured electronic spectra.

Efficient separation of conjugated polymers using a water soluble glycoprotein matrix: from fluorescence materials to light emitting devices.

Optically active bio-composite blends of conjugated polymers or oligomers are fabricated by complexing them with bovine submaxilliary mucin (BSM) protein. The BSM matrix is exploited to host hydrophobic extended conjugated π-systems and to prevent undesirable aggregation and render such materials water soluble. This method allows tuning the emission color of solutions and films from the basic colors to the technologically challenging white emission. Furthermore, electrically driven light emitting biological devices are prepared and operated.

Effects of solvent properties on the spectroscopy and dynamics of alkoxy-substituted PPV oligomer aggregates.

Conjugated systems are frequently studied in their nanoaggregate form to probe the effects of solvent and of film formation on their spectral and dynamical properties. This article focuses on the emission spectra and dynamics of nanoaggregates of alkoxy-substituted PPV oligomers with the goal of interpreting the vibronic emission envelopes observed in these systems (J. Phys. Chem. C2009, 113, 18851-18862). The aggregates are formed by adding a nonsolvent such as methanol (MeOH) or water to a solution of the oligomers in a good solvent such as methyl tetrahydrofuran (MeTHF) or tetrahydrofuran (THF). The emission spectra of aggregates formed using either of these combinations exhibit a vibronic pattern in which the ratio of the intensity of highest-energy band to that of the lower energy peaks depends strongly on the ratio of good to poor solvent. In aggregates formed from MeTHF:MeOH, this was shown to be due to the presence of both aggregate-like and monomer-like emitters forming a "core" and surrounding "shell"-like structure, respectively, within a single aggregate (J. Phys. Chem. C2011, 115, 15607-15616). In support of this model, the monomer-like emission is shown here to be significantly decreased by changing the solvent pair to the more polar THF:water. This suggests that nanoaggregates formed in THF:water contain a much smaller proportion of monomer-like chains than those formed in MeTHF/MeOH, as would be expected from using a more highly polar nonsolvent. Results from bulk steady-state and time-resolved emission measurements as well as fluorescence lifetime imaging microscopy (FLIM) of the aggregates are shown to be consistent with this interpretation.

Electric-field-induced fluorescence quenching in polyfluorene, ladder-type polymers, and MEH-PPV: evidence for field effects on internal conversion rates in the low concentration limit.

Electric field-induced fluorescence quenching has been measured for a series of conjugated polymers with applications in organic light-emitting diodes. Electrofluorescence measurements on isolated chains in a glassy matrix at 77 K show that the quenching efficiency for poly[2-methoxy-5-(2-ethylhexyloxy)-p-phenylenevinylene] (MEH-PPV) is an order of magnitude larger than that for either a ladder-type polymer (MeLPPP) or polyfluorene (PFH). This effect is explained in terms of the relatively high probability of field-enhanced internal conversion deactivation in MEH-PPV relative to either MeLPPP or PFH. These data, obtained under dilute sample conditions such that chain-chain interactions are minimal, are contrasted with the much higher quenching efficiencies observed in the corresponding polymer films, and several explanations for the differences are considered. In addition, the values of the change in dipole moment and change in polarizability on excitation (|Δµ| and tr(Δα), respectively) are reported, and trends in these values as a function of molecular structure and chain length are discussed.

Electrofluorescence of MEH-PPV and its oligomers: evidence for field-induced fluorescence quenching of single chains.

Electrofluorescence (Stark) spectroscopy has been used to measure the trace of the change in polarizability (trDeltaalpha) and the absolute value of the change in dipole moment (|Deltamu|) of the electroluminescent polymer poly[2-methoxy,5-(2'-ethyl-hexoxy)-1,4-phenylene vinylene] (MEH-PPV) and several model oligomers in solvent glass matrixes. From electrofluorescence, the measured values of trDeltaalpha increase from 500 +/- 60 A(3) in OPPV-5 to 2000 +/- 200 A(3) in MEH-PPV. The good agreement found between these values and those measured by electroabsorption suggests the electronic properties do not differ strongly between absorption and emission, in contrast to earlier predictions. Evidence of electric-field-induced fluorescence quenching of MEH-PPV in dilute solvent glasses was found. When normalized to the square of the applied electric field, the magnitude of quench is comparable to that reported in the literature for thin films of MEH-PPV. In addition, fluorescence quenching was also observed in the oligomers with a magnitude that increases with increasing chain length. By using the values of trDeltaalpha measured by electrofluorescence, a model is developed to qualitatively explain the chain length dependence to the fluorescence quench observed in the oligomers as a function of exciton delocalization along the oligomer backbone. Various explanations for the origin of this quenching behavior and its chain length dependence are considered.