Revealing Order and Disorder in Films and Single Crystals of a Thiophene-Based Oligomer by Optical Spectroscopy
Sajedeh Motamen, Dominic Raithel, Richard Hildner, Khosrow Rahimi, Thibaut Jarrosson, Françoise Serein-Spirau, Laurent Simon, and Günter Reiter. ACS Photonics 3 (2016) 2315–2323
Depending on processing conditions, ordered microstructures of conjugated oligomers or polymers exhibit variable amounts of grain boundaries, lattice disorder and amorphous (disordered) regions. These structural details can be determined very precisely. Their correlations with optical or electronic properties, however, are very difficult to establish, because e.g., optical spectra are usually averaged over regions with different degrees of disorder. In an attempt to facilitate the interpretation of optical spectra, we performed systematic studies on thin films and μm-sized single crystals of thiophene-based conjugated molecules, which allowed identifying the relative contributions of ordered and disordered regions in optical emission spectra. A detailed multi-peak analysis of the emission spectra showed that the peak positions, the energies of the emitted photons, showed only minor changes, independent if highly ordered or rather disordered samples were examined. However, the relative emission intensity changed significantly between samples. In particular, for highly ordered single crystals the purely electronic 0-0 transition nearly vanished, i.e., it was essentially optically forbidden as theoretically predicted. Thus, changes in emission probability are correlated with the degree of structural order in semiconducting conjugated systems and provide a possibility to quantify structural order.