Nanoscale Domain Imaging of All-Polymer Organic Solar Cells by Photo-Induced Force Microscopy.

Rapid nanoscale imaging of the bulk heterojunction layer in organic solar cells is essential to the continued development of high-performance devices. Unfortunately, commonly used imaging techniques such as tunneling electron microscopy (TEM) and atomic force microscopy (AFM) suffer from significant drawbacks. For instance, assuming domain identity from phase contrast or topographical features can lead to inaccurate morphological conclusions. Here we demonstrate a technique known as photo-induced force microscopy (PiFM) for imaging organic solar cell bulk heterojunctions with nanoscale chemical specificity. PiFM is a relatively recent scanning probe microscopy technique that combines an AFM tip with a tunable infrared laser to induce a dipole for chemical imaging. Coupling the nanometer resolution of AFM with the chemical specificity of a tuned IR laser, we are able to spatially map the donor and acceptor domains in a model all-polymer bulk heterojunction with resolution approaching 10 nm. Domain size from PiFM images is compared to bulk-averaged results from resonant soft X-ray scattering, indicating excellent quantitative agreement. Further, we demonstrate that in our all-polymer system, the AFM topography, AFM phase, and PiFM show poor correlation, highlighting the need to move beyond standard AFM for morphology characterization of bulk heterojunctions.

Solution-Phase Conformation and Dynamics of Conjugated Isoindigo-Based Donor-Acceptor Polymer Single Chains.

Conjugated polymers are the key material in thin-film organic optoelectronic devices due to the versatility of these molecules combined with their semiconducting properties. A molecular-scale understanding of conjugated polymers is important to the optimization of the thin-film morphology. We examine the solution-phase behavior of conjugated isoindigo-based donor-acceptor polymer single chains of various chain lengths using atomistic molecular dynamics simulations. Our simulations elucidate the transition from a rod-like to a coil-like conformation from an analysis of normal modes and persistence length. In addition, we find another transition based on the solvent environment, contrasting the coil-like conformation in a good solvent with a globule-like conformation in a poor solvent. Overall, our results provide valuable insights into the transition between conformational regimes for conjugated polymers as a function of both the chain length and the solvent environment, which will help to accurately parametrize higher level models.