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.