Luca Beverina, Christian Ruzié, Martin Kaltenegger, Roland Resel, Tommaso Salzillo, Adrián Tamayo, Alessandro Sanzone, Marta Mas-Torrent, Guillaume Schweicher, Sebastian Hofer, Johanna Unterkofler, Yves Geerts, Hofer S., Unterkofler J., Kaltenegger M., Schweicher G., Ruzie C., Tamayo A., Salzillo T., Mas-Torrent M., Sanzone A., Beverina L., Geerts Y.H., Resel R., Hofer, S, Unterkofler, J, Kaltenegger, M, Schweicher, G, Ruzie, C, Tamayo, A, Salzillo, T, Mas-Torrent, M, Sanzone, A, Beverina, L, Geerts, Y, Resel, R, Fonds de la Recherche Scientifique (Fédération Wallonie-Bruxelles), Research Foundation - Flanders, Austrian Science Fund, Communauté Française de Belgique, Fédération Wallonie-Bruxelles, Ministerio de Ciencia, Innovación y Universidades (España), and Generalitat de Catalunya
The molecule 2-decyl-7-phenyl-[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-10) is an organic semiconductor with outstanding performance in thin-film transistors. The asymmetric shape of the molecule causes an unusual phase behavior, which is a result of a distinct difference in the molecular arrangement between the head-to-head stacking of the molecules versus head-to-tail stacking. Thin films are prepared at elevated temperatures by crystallization from melt under controlled cooling rates, thermal-gradient crystallization, and bar coating at elevated temperatures. The films are investigated using X-ray diffraction techniques. Unusual peak-broadening effects are found, which cannot be explained using standard models. The modeling of the diffraction patterns with a statistic variation of the molecules reveal that a specific type of molecular disorder is responsible for the observed peak-broadening phenomena: the known head-to-head stacking within the crystalline phase is disturbed by the statistic integration of reversed (or flipped) molecules. It is found that 7–15% of the molecules are integrated in a reversed way, and these fractions are correlated with cooling rates during the sample preparation procedure. Temperature-dependent in situ experiments reveal that the defects can be healed by approaching the transition from the crystalline state to the smectic E state at a temperature of 145 °C. This work identifies and quantifies a specific crystalline defect type within thin films of an asymmetric rodlike conjugated molecule, which is caused by the crystallization kinetics., This work was supported by the Fonds de la Recherche Scientifique (FNRS) and the Fonds voor Wetenschappelijk Onderzoek – Vlanderen (FWO) under EOS project 30489208 and the Austrian Science Fund (FWF): [P30222]. YG is also thankful to FNRS for financial support through research projects BTBT n° 2.4565.11, Phasetrans n° T.0058.14, Pi-Fast n° T.0072.18, and 2D to 3D No. 30489208. Financial supports from the French Community of Belgian (ARC n° 20061) and by the Walloon Region (WCS No. 1117306, SOLIDYE n° 1510602) are also acknowledged. G.S. acknowledges postdoctoral fellowship support from the FNRS. M.M. thanks the Spanish Ministry project GENESIS PID2019-111682RB-I00, the “Severo Ochoa” Programme for the Centers of Excellence in R&D (FUNFUTURE, CEX2019-000917-S), and the Generalitat de Catalunya (2017-SGR-918). A.T. is enrolled in the Materials Science PhD program of Universitat Autònoma de Barcelona and acknowledges FPU fellowship from the Spanish Ministry. The large-scale facility Elettra, Trieste, Italy, provided synchrotron radiation for grazing incidence X-ray diffraction experiments at the beamline XRD1.