Sub-micron phase coexistence in small-molecule organic thin films revealed by infrared nano-imaging

Abstract

Controlling the domain size and degree of crystallization in organic films is highly important for electronic applications such as organic photovoltaics, but suitable nanoscale mapping is very difficult. Here we apply infrared-spectroscopic nano-imaging to directly determine the local crystallinity of organic thin films with 20-nm resolution. We find that state-of-the-art pentacene films (grown on SiO ₂ at elevated temperature) are structurally not homogeneous but exhibit two interpenetrating phases at sub-micrometre scale, documented by a shifted vibrational resonance. We observe bulk-phase nucleation of distinct ellipsoidal shape within the dominant pentacene thin-film phase and also further growth during storage. A faint topographical contrast as well as X-ray analysis corroborates our interpretation. As bulk-phase nucleation obstructs carrier percolation paths within the thin-film phase, hitherto uncontrolled structural inhomogeneity might have caused conflicting reports about pentacene carrier mobility. Infrared-spectroscopic nano-imaging of nanoscale polymorphism should have many applications ranging from organic nanocomposites to geologic minerals.

Abstract

The grain boundaries between two coexisting phases in organic semiconductor pentacene are expected to obstruct charge transport in its thin-film devices. Westermeier et al. use infrared-spectroscopic nano-imaging to show an interlocking morphology, which is uncorrelated with its grain structures.