Molecular packing in laterally directed solution deposition is a strong function of variables such as printing speed, substrate temperature, and solution concentration. Knowledge of the ordering mechanisms impacts on the development of new processes and materials for improved electronic devices. Here, we present real-time synchrotron x-ray scattering results combined with optical video microscopy, revealing the stages of ordering during the deposition of organic thin films via hollow capillary writing. Limited long range ordering is observed during the initial crystallization, but it gradually develops over 3-4 s for a range of deposition conditions. Buckling of thin films is typically observed for deposition above room temperature. We infer that compressive stress originates from thermal transients related to solvent evaporation on timescales similar to the development of long range ordering. Under optimized conditions, elimination of cracks and other structural defects significantly improves the average charge carrier mobility in organic field-effect transistors. (C) 2013 Author(s).