Polar Polymorphism: A New Intermediate Structure toward the Thin-Film Phase in Asymmetric Benzothieno[3,2-][1]-benzothiophene Derivatives.

Understanding structure and polymorphism is relevant for any organic device optimization, and it is of particular relevance in 7-decyl-2-phenyl[1]benzothieno[3,2-][1]benzothiophene (Ph-BTBT-10) since high carrier mobility in Ph-BTBT-10 thin films has been linked to the structural transformation from the metastable thin-film phase to the thermodynamically stable bilayer structure via thermal annealing. We combine here a systematic nanoscale morphological analysis with local Kelvin probe force microcopy (KPFM) that demonstrates the formation of a polar polymorph in thin films as an intermediate structure for thicknesses lower than 20 nm. The polar structure develops with thickness a variable amount of structural defects in the form of individual flipped molecules (point defects) or sizable polar domains, and evolves toward the reported nonpolar thin-film phase. The direct experimental evidence is supported by electronic structure density functional theory calculations. The structure of the film has dramatic effects on the electronic properties, leading to a decrease in the film work function (by up to 1 eV) and a considerable broadening of the occupied molecular orbitals, attributed to electrostatic disorder. From an advanced characterization point of view, KPFM stands out as a valuable tool for evaluating electrostatic disorder and the conceivable emergence of polar polymorphs in organic thin films. The emergence of polar assemblies introduces a critical consideration for other asymmetric BTBT derivatives, which may be pivotal to understanding the structure-property relationships in organic field-effect transistors (OFETs). A precise determination of any polar assemblies close to the dielectric interface is critical for the judicious design and upgrading of high-performance OFETs.