Controlling microstructure of pentacene derivatives by solution processing: impact of structural anisotropy on optoelectronic properties.

The consideration of anisotropic structural properties and their impact on optoelectronic properties in small-molecule thin films is vital to understand the performance of devices incorporating crystalline organic semiconductors. Here we report on the important relationship between structural and optoelectronic anisotropy in aligned, functionalized-pentacene thin films fabricated using the solution-based zone-casting technique. The microstructure of thin films composed of 6,13-bis(triisopropylsilylethynyl)pentacene (TIPS-pentacene) and 6,13-bis(triethylsilylethynyl)pentacene (TES-pentacene) is systematically controlled by varying the casting speed. By controlling the structural alignment, we were able to experimentally decouple, for the first time in these films, an intramolecular absorption transition dipole (at ∼440 nm) oriented close to the pentacene short axis and an intermolecular absorption transition dipole (at ∼695 nm) oriented predominantly along the conjugated pentacene-pentacene core stacking axis (crystallographic a-axis) in both films. Using the intermolecular absorption as a signature for intermolecular delocalization, much higher optical dichroism was obtained in TES-pentacene (16 ± 6) than TIPS-pentacene (3.2 ± 0.1), which was attributed to the 1D packing structure of TES-pentacene compared to the 2D packing structure of TIPS-pentacene. This result was also supported by field-effect mobility anisotropy measurements of the films, with TES-pentacene exhibiting a higher anisotropy (∼21-47, depending on the casting speed) than TIPS-pentacene (∼3-10).