Groves, C. (2012) 'The relative importance of domain size, domain purity and domain interfaces to the performance of bulk-heterojunction organic photovoltaics.', Energy and environmental science., 5 (6). pp. 7657-7663. Further information on publisher's website:http://dx.doi.org/10.1039/C2EE21327CPublisher's copyright statement:Additional information: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-profit purposes provided that:• a full bibliographic reference is made to the original source• a link is made to the metadata record in DRO• the full-text is not changed in any wayThe full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. performance due to the difficulty of demonstrating causal links between properties and performance. As a result, the relative importance of size and purity of domains, and the interfaces between, is not generally known. In this paper we use morphological and charge transport modeling techniques to show unambiguously the effect of these features on the performance of OPVs. Surprisingly we find that the commonly reported 'optimum' domain size of ~10nm is only of significant benefit in structures with pure domains, and further that sharpening the interface between domains is of greater benefit to performance. We also show how changing the interaction parameter of the blend components is a versatile technique to achieve sharper interfaces and higher OPV performance. More generally, we have demonstrated a combination of modeling techniques that are able to give an indication of answers to questions relevant to OPVs that would be difficult to achieve experimentally. ABSTRACTThe domain size, domain purity and interfacial width between domains for a bulk heterojunction are controllably altered through use of Cahn-Hilliard modeling and their relative effect on OPV performance is predicted using Monte Carlo modeling. It is found that locally-sharp, well-connected domains of only 4nm extent out perform morphologies with broadened interfaces and/or impure domains even when domain sizes were at the 'optimum' size of ~10nm. More generally, these data provide information on the most effective method to optimize the as-cast bulk heterojunction morphology depending upon initial domain purity and the nature of interfaces between domains. Further, it indicates why morphology optimization is more effective for some blends than others. It is shown that the quench depth of the blend can be used as a general technique to control the interfacial structure of the morphology and realize substantial increases in short circuit photocurrent.3

We report on an experimental study of the self-organization and phase behavior of hairy-rod -conjugated branched side-chain polyfluorene, poly͓9,9-bis͑2-ethylhexyl͒-fluorene-2,7-diyl͔-i.e., poly͓2,7-͑9,9-bis͑2-ethylhexyl͒fluorene͔ ͑PF2/6͒-as a function of molecular weight ͑M n ͒. The results have been compared to those of phenomenological theory. Samples for which M n = 3 -147 kg/ mol were used. First, the stiffness of PF2 / 6, the assumption of the theory, has been probed by small-angle neutron scattering in solution. Thermogravimetry has been used to show that PF2 / 6 is thermally stable over the conditions studied. Second, the existence of nematic and hexagonal phases has been phenomenologically identified for lower and higher M n ͑LMW, M n Ͻ M n * and HMW, M n Ͼ M n * ͒ regimes, respectively, based on free-energy argument of nematic and hexagonal hairy rods and found to correspond to the experimental x-ray diffraction ͑XRD͒ results for PF2 / 6. By using the lattice parameters of PF2 / 6 as an experimental input, the nematic-hexagonal transition has been predicted in the vicinity of glassification temperature ͑T g ͒ of PF2 / 6. Then, by taking the orientation parts of the free energies into account the nematic-hexagonal transition has been calculated as a function of temperature and M n and a phase diagram has been formed. Below T g of 80°C only ͑frozen͒ nematic phase is observed for M n Ͻ M n * =10 4 g / mol and crystalline hexagonal phase for M n Ͼ M n * . The nematic-hexagonal transition upon heating is observed for the HMW regime depending weakly on M n , being at 140-165°C for M n Ͼ M n * . Third, the phase behavior and structure formation as a function of M n have been probed using powder and fiber XRD and differential scanning calorimetry and reasonable semiquantitative agreement with theory has been found for M n ജ 3 kg/ mol. Fourth, structural characteristics are widely discussed. The nematic phase of LMW materials has been observed to be denser than high-temperature nematic phase of HMW compounds. The hexagonal phase has been found to be paracrystalline in the ͑ab0͒ plane but a genuine crystal meridionally. We also find that all these materials including the shortest 10-mer possess the formerly observed rigid five-helix hairy-rod molecular structure.

This account highlights recent progress towards understanding the complex hierarchical levels of solid‐state structure in a prototypical helical hairy‐rod polyfluorene, poly[9,9‐bis(2‐ethylhexyl)fluorene‐2,7‐diyl] (or PF2/6). This branched‐side‐chain containing polyfluorene undergoes a systematic intermolecular self‐assembly and liquid‐crystalline phase behavior in combination with uniaxial and biaxial alignment. The latter processes yield full three‐dimensional orientation of the crystallites and polymer chains. Also reviewed are the impact of the molecular structure and phase behavior on surface morphology, anisotropic film formation, and, ultimately, the overall impact of these physical attributes on optical constants. This particular polyfluorene also represents a model system for demonstrating the applicability of mean‐field theory in detailing the self‐organization of aligned hairy‐rod block‐copolymer systems. These results of PF2/6 are compared to those of other archetypical π‐conjugated hairy‐rod polymers. General guidelines of how molecular weight influences nanostructure, phase behavior, alignment, and surface morphology are given.

The structural investigation of poly(9,9-bis(2-ethylhexyl)fluorene-2,7-diyl) (PF2/6) in aligned thin films is presented. Formation of a thickness dependent triaxial texturing is identified in thermotropically aligned films. X-ray reflectivity measurements reveal good macroscopic quality, and polarized photoluminescence and dichroic ratios in absorption indicate clear axial alignment. Grazing-incidence X-ray diffraction shows axially aligned mesomorphic structure with a distinct arrangement of helices and large correlation lengths, indicating a high local lateral order. Theoretical models produced using molecular mechanics methods suggest 5/2-helicity. The polymer chains are parallel to the substrate in the c direction. In particular, the hexagonal-like cells are flattened in the direction of the surface normal and reveal two kinds of coexistent crystallites, a multiple orientation where the greater proportion of the crystallites have one crystal axis a perpendicular to the substrate surface, whereas a smaller proportion is aligned with the crystal axis a parallel to the surface. In thinner films the former class of orientation is usually dominant, while the proportion of the parallel orientation type increases with prolonged annealing.