Quantitative analysis of phase formation and growth in ternary mixtures upon evaporation of one component.

We perform a quantitative analysis of Monte Carlo simulation results of phase separation in ternary blends upon evaporation of one component. Specifically, we calculate the average domain size and plot it as a function of simulation time to compute the exponent of the obtained power law. We compare and discuss results obtained by two different methods, for three different models: two-dimensional (2D) binary-state model (Ising model), 2D ternary-state model with and without evaporation. For the ternary-state models, we study additionally the dependence of the domain growth on concentration, temperature and initial composition. We reproduce the expected 1/3 exponent for the Ising model, while for the ternary-state model without evaporation and for the one with evaporation we obtain lower values of the exponent. It turns out that phase separation patterns that can form in this type of systems are complex. The obtained quantitative results give valuable insights towards devising computable theoretical estimations of size effects on morphologies as they occur in the context of organic solar cells.

An experimental setup for dip-coating of thin films for organic solar cells under microgravity conditions.

We report the design and testing of a custom-built experimental setup for dip-coating from volatile solutions under microgravity conditions onboard an aircraft. Function and safety considerations for the equipment are described. The equipment proved to work well, both concerning the safety and the preparation of thin films. No leakage of the solvents, nor the solvent vapors, was detected, not even in a situation with a fluctuating gravitational field due to bad weather conditions. We have shown that the equipment can be used to prepare thin films of polymer blends, relevant for organic solar cells, from solution in a feasible procedure under microgravity conditions. The prepared films are similar to the corresponding films prepared under 1 g conditions, but with differences that can be related to the absence of a gravitational field during drying of the applied liquid coating. We report on some introductory results from the characterization of the thin films that show differences in film morphology and structure sizes.

Using Solubility Parameters to Model More Environmentally Friendly Solvent Blends for Organic Solar Cell Active Layers.

To facilitate industrial applications, as well as for environmental and health purposes, there is a need to find less hazardous solvents for processing the photoactive layer of organic solar cells. As there are vast amounts of possibilities to combine organic solvents and solutes, it is of high importance to find paths to discriminate among the solution chemistry possibilities on a theoretical basis. Using Hansen solubility parameters (HSP) offers such a path. We report on some examples of solvent blends that have been found by modelling HSP for an electron donor polymer (TQ1) and an electron acceptor polymer (N2200) to match solvent blends of less hazardous solvents than those commonly used. After the theoretical screening procedure, solubility tests were performed to determine the HSP parameters relevant for the TQ1:N2200 pair in the calculated solvent blends. Finally, thin solid films were prepared by spin-coating from the solvent blends that turned out to be good solvents to the donor-acceptor pair. Our results show that the blend film morphology prepared in this way is similar to those obtained from chloroform solutions.

Fullerene Aggregation in Thin Films of Polymer Blends for Solar Cell Applications.

We report on the effects of the film morphology on the fluorescence spectra for a thin film including a quinoxaline-based co-polymer (TQ1) and a fullerene derivative ([6,6]-phenyl-C71-butyric acid methyl ester-PC70BM). The ratio between the polymer and the fullerene derivative, as well as the processing solvent, were varied. Besides the main emission peak at 700 nm in the fluorescence spectra of thin films of this phase-separated blend, a broad emission band is observed with a maximum at 520⁻550 nm. The intensity of this emission band decreases with an increasing degree of mixing in the film and becomes most prominent in thicker films, films with high PC70BM content, and films that were spin-coated from solvents with lower PC70BM solubility. We assign this emission band to aggregated PC70BM.

Latex diffusion at high volume fractions studied by fluorescence microscopy.

The behavior of fluorescent latex probes (radii 0.05, 0.1, and 0.5 mum) in latex host particle suspensions was investigated by fluorescence microscopy with image analysis. The volume fraction of the host latex was varied between 0 and 0.50. A careful statistical analysis was performed to examine the accuracy of the fluorescence microscopy method, from which the direct observation of the Brownian motion gives the diffusion coefficient. The method was found to meet all statistical requirements. From rheological measurements, the maximum volume fraction and the intrinsic viscosity can be obtained. The Krieger-Dougherty equation can be used for the prediction of sample viscosities. The predicted viscosities were used to obtain the theoretical diffusion coefficients with the Stoke-Einstein equation. When comparing the theoretical diffusion coefficients with the experimental ones, it turned out that all models tested yielded acceptable predictions of the diffusion coefficients.

Dynamic fluorescence microscopy as a feasible technique for estimating the diffusion coefficients of small particles in the presence of additives.

The Brownian motion of carboxylated polystyrene latex, labeled with fluorescent probe molecules, at low concentrations in aqueous solutions was investigated by dynamic fluorescence microscopy. For all three latex radii, i.e., 0.5, 0.265, and 0.1 mum, the estimated diffusion coefficients correspond well with the theoretical predictions if thermal and electrostatic contributions are included in the discussions. It was also possible to discriminate latex interactions with an added polymer. Added polyethylene glycol showed no or very weak interaction with the latex until the polymer overlap concentration was reached, at which the formation of a polymer network slowed down the latex diffusion. Polyvinylpyrrolidone, on the other hand, had a more pronounced interaction with the polystyrene latex and slowed down the diffusion even at polymer concentrations in the ppm range. The overall conclusion is that fluorescence microscopy is a feasible method for the study of the dynamic behavior of small particles in solution.

Tuning of the alpha-terthiophene radical cation coupling reaction using mixed micelles with varying charge density.

The photophysics and photochemistry of alpha-terthiophene (alphaT), compartmentalized in mixed nonionic/anionic micelles, have been investigated with focus on the influence of the micellar surface charge density on the formation of the radical coupling product alpha-hexathiophene (alphaH). By varying the ratio of nonionic-to-anionic surfactants, and assuming ideal mixing, the charge density of the mixed micelles was varied. From Poisson-Boltzmann calculations, performed using the cell model, the electrostatic potential and the counterion activity were estimated as a function of the distance from the micellar surface. Upon excitation, the triplet state of alphaT is formed, from which the alphaT radical cation can be formed by absorption of a second photon. The radical cation can form alphaH if it encounters another alphaT radical cation. Under the experimental conditions used, this implies that the alphaH formation only occurs if the compartmentalized radical cation is able to migrate from its host micelle to another micelle, either via the surrounding bulk or by fusion of two micelles followed by mixing of their contents before micellar fission. The formation yield of the radical cation depends on the charge density of the mixed micelle; a lower charge density, that is, an increased amount of nonionic surfactant, lowers the yield. The yield of the coupling product alphaH, however, does not follow the same trend. A maximum yield of alphaH is found at intermediate nonionic surfactant molar ratios. This behavior is understood in terms of the Poisson-Boltzmann simulation results and by comparing charge-density changes as a function of molar fraction with the changes in counterion activity. The alphaH yield is a result of the balance between an increased possibility of radical cation bulk migration and a lowered electrostatic stabilization of the radical.

Supramolecular control of two-dimensional phase behavior.

We have used directed two-component self-assembly to "pattern" organic monolayers on the nanometer scale at the liquid/solid interface. The ability of the scanning tunneling microscope to investigate structural details in these adlayers was used to gain insight into the two-component two-dimensional phase behavior. The components are symmetrically alkylated bisurea derivatives (R1-urea-spacer-urea-R2; R1, R2=alkyl, spacer=alkyl or bisthiophene). The bisthiophene unit acts as a marker and its bisurea derivative (T2) is a component in all the mixtures investigated. By varying the position of the hydrogen-bond forming urea groups along the molecule and the length of the alkyl chains of the other components, the effect of 1) hydrogen bonding, 2) molecule length, 3) odd-even effects, and 4) shape complementarity on the two-dimensional phase behavior was investigated. Insight into the effect of these parameters leads to the control of the two-dimensional patterning: from randomly intermixed systems to phase separation.