The understanding of the charge transport depending on crystalline structure in organic semiconductors is an important aspect of their functionality in different organic electronic applications. For this reason we performed in situ grazing incidence X-ray diffraction (GIXD) studies to trace the solidification. Simultaneously applying the voltage to the thiophene-based oligomer system the current response was measured. The complex behaviour of the solidification process was monitored from the structure and electrical performance and the highest current was observed for the final solid film. Real time studies revealed that for the oligomers the high crystallinity is a key factor for the improvement of the charge transport.
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