Submolecular Resolution Imaging of P3HT:PCBM Nanostructured Films by Atomic Force Microscopy: Implications for Organic Solar Cells.

The efficiency of organic bulk-heterojunction (BHJ) solar cells depends greatly on both the bulk and surface structure of the nanostructured bicontinuous interpenetrating network of materials, known as the active layer. The morphology of the top layer of a coated film is often resolved at the scale of a few nanometers, but fine details of the domains and the order within them are more difficult to identify. Here, we report a high-resolution atomic force microscopy (AFM) investigation of various stoichiometries of the well-studied poly(3-hexylthiophene):[6,6]-phenyl C61 butyric acid methyl ester (P3HT:PCBM) active layer mixture. Images of the surface were obtained using AC-mode AFM exciting higher-order resonance frequencies of a standard silicon probe, a promising technique for acquiring real-space images of organic-based thin films with nanoscale and even submolecular resolution. We provide firm evidence of the nanoscale organization of the P3HT polymer and of the P3HT:PCBM stoichiometric mixtures at the surface-air interface of the BHJ architecture. Our study shows the characteristic periodicity of the regioregular P3HT identified in the nanoscale domain areas with submolecular resolution. Such areas are then distorted in place when adding different quantities of PCBM forming stoichiometric mixtures. When the samples were exposed to ambient light, the morphologies were very different, and submolecular resolution was not achieved. This approach is shown to provide a precise view of the active layer's nanostructure and will be useful for studies of other materials as a function of various parameters, with particular attention to the role of the acceptor in tuning morphology for understanding optimum performance in organic photovoltaic devices.

Natural optical activity as the origin of the large chiroptical properties in π-conjugated polymer thin films.

Polymer thin films that emit and absorb circularly polarised light have been demonstrated with the promise of achieving important technological advances; from efficient, high-performance displays, to 3D imaging and all-organic spintronic devices. However, the origin of the large chiroptical effects in such films has, until now, remained elusive. We investigate the emergence of such phenomena in achiral polymers blended with a chiral small-molecule additive (1-aza[6]helicene) and intrinsically chiral-sidechain polymers using a combination of spectroscopic methods and structural probes. We show that - under conditions relevant for device fabrication - the large chiroptical effects are caused by magneto-electric coupling (natural optical activity), not structural chirality as previously assumed, and may occur because of local order in a cylinder blue phase-type organisation. This disruptive mechanistic insight into chiral polymer thin films will offer new approaches towards chiroptical materials development after almost three decades of research in this area.