Microstructural Evolution of the Thin Films of a Donor-Acceptor Semiconducting Polymer Deposited by Meniscus-Guided Coating

Crucial to the development and refinement of organic electronics is a fundamental understanding of how deposition processes affect the active material's resulting microstructure in the thin film. Meniscus-guided coating (MGC) methods are attractive because of their amenability to high-throughput, industrially relevant continuous processes like roll-to-roll deposition, but the mechanism of solid film formation has not been elucidated and is valuable for the precise control of thin-film morphology and thus ultimate device performance. In this work, we investigate the microstructural evolution of thin films of a diketopyrrolopyrrole-terthiophene donor-acceptor polymer semiconductor using both in situ and ex situ X-ray diffraction methods. On the basis of a comparison of disorder between the film bulk and the top surface and a depth profiling of the out-ofplane orientation of crystallites, we find that faster coating speeds introduce more disorder into the resulting films because the stochastic nucleation of disordered crystallites at the meniscus air-liquid interface becomes more dominant than substratemediated nucleation. Our results suggest that there exist three separate deposition regimes-namely the shear-dominate, disorder-dominate, and Landau-Levich-Derjaguin regimes-revealed by observing both polymer alignment via dry film thickness and optical dichroism, a property sensitive to the flow and shear fields. At low coating speeds, the shear strain imparted upon the solution directly induces polymer alignment, causing an increase in dichroism as a function of coating speed. When solvent evaporation becomes too rapid as coating speeds increase, a decrease in the dichroic ratio is observed before the classical Landau-Levich-Derjaguin regime occurs at the highest coating speeds, resulting in isotropic films. The preservation of out-ofplane crystalline texture throughout the thickness of the films is seen only for lower coating speeds, and a study of different deposition temperatures similarly indicates that the lower overall solvent evaporation is conducive to this process. Increased paracrystalline disorder (i.e., peak broadening) is observed by grazing-incidence wide-angle X-ray diffraction at the top interface of the dry films and at higher coating speeds. Together, these results indicate that more rapid solvent evaporation at higher coating speeds causes increased disorder, which can cause the nucleation of misaligned crystallites, affect the dichroic ratio, and may frustrate the alignment of polymer molecules in the amorphous regions of the film. Because the polymer studied and the deposition technique used are representative models, these results are likely general for aggregating, semicrystalline donor- acceptor polymers deposited with MGC.