Muhammet E. Köse

Charge transport simulations in conjugated dendrimers.

We present here a theoretical methodology that exploits quantum mechanical calculations, molecular mechanics calculations, and Monte Carlo simulations to predict the time-of-flight measurement mobilities in films of phenyl-cored conjugated thiophene dendrimers. Our aim is to reveal structure-property relationships in amorphous films of organic pi-conjugated materials. The simulations show that both hole and electron mobilities increase with the size of dendrimer, and that the former is larger than latter in all dendrimers. Internal reorganization energies are inversely correlated with the mobilities. Our simulations also indicate that dendrimers have small density of states for energetic disorder (<60 meV), and both hole and electron mobilities possess weak electric field dependence. We examine the influence of external reorganization energy as well as the possible trap sites on charge transport in these materials.

Evaluation of acceptor strength in thiophene coupled donor-acceptor chromophores for optimal design of organic photovoltaic materials.

A series of thiophene coupled acceptors were systematically investigated at the density functional theory level to reveal structure-property relationships for building blocks of materials used in organic photovoltaic applications. All of the acceptor groups studied in this work retain their aromaticity when coupled to thiophene groups as estimated from their aromatic stabilization energies. However, pure chains of acceptors may adopt quinoidal geometry along the conjugated backbone depending on the structure of interest. Spearman rank order correlation has been used to assess the relationships between the computed variables such as highest occupied molecular orbital, lowest unoccupied molecular orbital, E(g), oscillator strength, exciton binding energy, aromatic stabilization energy, etc. The relative acceptor strengths were plotted and electrostatic potential maps were generated to examine the charge distribution over the chromophores. It has been found that there is no correlation between acceptor strength and electron withdrawing ability of the acceptor. Electron rich and highly electronegative atoms within acceptor groups mainly affect the charge distribution over the acceptor geometry. Exciton binding energy increases with the increasing aromatic character of the acceptor group. The acceptor strength is inversely correlated with the oscillator strength for the lowest excited state transition.

Synthesis, photophysics, and photovoltaic properties of low-band gap conjugated polymers based on thieno[3,4-c]pyrrole-4,6-dione: a combined experimental and computational study

Four novel donor–acceptor (D–A) alternating copolymers were designed and successfully synthesized by the palladium-catalyzed Stille coupling and Suzuki coupling reactions. Utilizing thieno[3,4-c]pyrrole-4,6-dione (TPD) as an acceptor comonomer coupled with dialkoxybithiophene or cyclopentadithiophene as the donor gave polymers PTBT and PTCT. Employing carbazole as the donor and the dithiophene-substituted TPD serving as the acceptor monomers yielded polymers PTC1 and PTC2. Owing to the various strengths of electronic coupling between the donors and the acceptor unit, the band gaps of these polymers can be adjusted from 1.57 to 1.90 eV. Due to the different electron-donor ability of dialkoxybithiophene, cyclopentadithiophene, and carbazole, the HOMO energy levels of polymers were tuned from −5.34 to −5.67 eV, while LUMO levels remained relatively unchanged. The theoretical calculations provided insight to the observed photophysical properties of these polymers. Theoretically estimated band gaps and oxidation potentials correlate well with the experimental data. Carrier mobility and photovoltaic properties of TPD polymers were also investigated for which 1.3% power conversion efficiency was obtained from a blend of PTCT:PC71BM (1:2) bulk-heterojunction device.

Exciton migration in conjugated dendrimers: a joint experimental and theoretical study.

We report a joint experimental and theoretical investigation of exciton diffusion in phenyl-cored thiophene dendrimers. Experimental exciton diffusion lengths of the dendrimers vary between 8 and 17 nm, increasing with the size of the dendrimer. A theoretical methodology is developed to estimate exciton diffusion lengths for conjugated small molecules in a simulated amorphous film. The theoretical approach exploits Fermis Golden Rule to estimate the energy transfer rates for a large ensemble of bimolecular complexes in random relative orientations. Utilization of Poissons equation in the evaluation of the Coulomb integral leads to very efficient calculation of excitonic couplings between the donor and the acceptor chromophores. Electronic coupling calculations with delocalized transition densities revealed efficient coupling pathways in the bulk of the material, but do not result in strong couplings between the chromophores which are calculated for more localized transition densities. The molecular structures of dendrimers seem to be playing a significant role in the magnitude of electronic coupling between chromophores. Simulated diffusion lengths correlate well with the experimental data. The chemical structure of the chromophore, the shape of the transition densities and the exciton lifetime are found to be the most important factors in determining the size of the exciton diffusion length in amorphous films of conjugated materials.

Intramolecular triplet energy transfer in anthracene-based platinum acetylide oligomers.

Platinum acetylide oligomers that contain an anthracene moiety have been synthesized and subjected to photophysical characterization. Spectroscopic measurement and DFT calculations reveal that both the singlet and triplet energy levels of the anthracene segment are lower than those of the platinum acetylide segment. Thus, the platinum acetylide segment acts as a sensitizer to populate the triplet state of the anthrancene segment via intramolecular triplet-triplet energy transfer. The objective of this work is to understand the mechanisms of energy-transfer dynamics in these systems. Fluorescence quenching and the dominant triplet absorption that arises from the anthracene segment in the transient absorption spectrum of Pt4An give clear evidence that energy transfer adopts an indirect mechanism, which begins with singlet-triplet energy transfer from the anthracene segment to the platinum acetylide segment followed by triplet-triplet energy transfer to the anthracene segment.

Theoretical study of torsional disorder in poly(3-alkylthiophene) single chains: intramolecular charge-transfer character and implications for photovoltaic properties.

The role of polymer chain morphology on the optoelectronic properties of polythiophenes is an ongoing investigation with the promise of improving organic photovoltaic performance. Chain morphology is predominantly affected by torsional disorder, which causes localization of holes and electrons in the conjugated backbone. Using the model compound oligo(3-methylthiophene), torsionally disordered oligomers were created to compare with a trans-planar oligomer such as found in crystalline poly(3-hexylthiophene). Low lying electronic excitations are calculated using TD-HF and TD-DFT with various long-range corrected functionals. Probability densities of electron and hole were constructed from natural transition orbitals, giving insight into localization and electron-hole overlap. Overlap is found to be substantially higher in disordered oligomers, indicating a stronger Coulombic interaction between electron and hole. Results suggest that improved photovoltaic performance with increased crystallinity is partially explained by stronger light absorption in crystalline polymers and a higher barrier to charge separation in disordered polymers.

Effective Solubilization of Single-Walled Carbon Nanotubes in THF Using PEGylated Corannulene Dispersant

PEG-derivatized corannulene compound has been found to be very effective in solubilizing single-walled carbon nanotubes in tetrahydrofuran. Solubilizing efficiency is close to the commonly used anionic surfactant, sodium dodecyl sulfate (SDS). Corannulene derivative has also been found to have a tendency to disperse metallic nanotubes more effectively than the SDS counterpart. Theoretical calculations predict higher dispersion interactions of corannulene backbone with the convex surface of nanotubes in comparison to those calculated with other commonly used polyaromatic hydrocarbon derivatives.

Pyrophosphate Sensor Based on Principal Component Analysis of Conjugated Polyelectrolyte Fluorescence

The pyrophosphate anion (PPi) plays an important role in biochemical processes. Therefore, a simple but reliable analytical technique is essential for selective detection of PPi in biochemical systems. Here, we present a principal component analysis (PCA) method for analytical determination of PPi concentration using a fluorescent conjugated polyelectrolyte (CPE) combined with a polyamine modifier. The CPE has anionic side chains and dissolves molecularly in water, as indicated by its structured fluorescence emission spectrum. However, addition of tris(3-aminoethyl)amine (tetraamine or N4) quenches the CPE fluorescence emission. Tetraamine, which is a polycation at neutral pH, binds multiple anionic CPE chains, leading to aggregate formation, resulting in aggregation-induced fluorescence quenching. Addition of PPi to the polymer–amine aggregate reverses the process, resulting in fluorescence recovery. The relatively higher concentration of PPi compared to that of the polymer allows it to effectively compete to bind the amine, thus releasing molecularly dissolved polymer chains. Fluorescence correlation spectroscopy of the P1/N4 complex and of P1/N4/PPi confirms the change in size of the CPE aggregates that occurs upon reversible aggregation. Application of PCA to the fluorescence emission data set of standard samples yields two principal components, which are used to create a predictive model for PPi analysis. The PCA method is able to directly determine the concentration of PPi with approximately 95% accuracy within the concentration range from 100 μM to 3 mM, without the need for a reference state as is typically needed for ratiometric fluorescence assays.

Amplified quenching of conjugated polymer nanoparticle photoluminescence for robust measurement of exciton diffusion length

A new method for measuring exciton diffusion length in nanoparticles (NPs) of conjugated materials is presented. Cationic acceptor dyes are used to quench the photoluminescence in NPs of the prototypical conjugated polymer poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV). Amplified quenching of MEH-PPV emission is observed with an initial Stern-Volmer constant in excess of 105 M−1. Stern-Volmer plots are nonlinear with two distinct quenching regimes, hinting saturation of NP surfaces with acceptor molecules at some point during titration experiments. Using an assumption that highly efficient quenching of excitons occurs after saturation with acceptors at the NP surfaces, the amount of maximum emission quenching can be compared with a model of exciton diffusion to determine exciton diffusion length. By assuming quenching efficiency above 80%, the measured three dimensional exciton diffusion length is estimated to be 12 ± 1 nm. This result is in the lower region of reported values ranging...

A Dual Luminophore Pressure Sensitive Paint: Eliminating the Temperature Interference in the Measurement of Oxygen Partial Pressure

Luminescence imaging, combined with pressure sensitive paint (PSP) is an optical method for measuring surface air pressure distributions on aerodynamic models in wind tunnels.1, 2 This method is of particular of interest to the aerospace industry for determining loads in aerodynamic prototype testing. When compared to conventional methods such as pressure tap measurements, luminescence imaging has the advantage of providing a non-invasive method to obtain full field surface air pressure distributions with high spatial resolution.