Directional crystallization of C8-BTBT-C8 thin films in a temperature gradient

A directional crystallization of the compound 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT-C8) based on a temperature gradient approach has been used as a post-deposition process to control the crystalline morphology of thin films. C8-BTBT-C8 films of arbitrary thicknesses have been fabricated by spin-coating and subjected to the directional crystallization process. Dewetting is prevented by the liquid crystal phase of C8-BTBT-C8, allowing the formation of flat and rather uniform thin films with large crystalline domains. Spin-coating concentration, gradient magnitude, and cooling rate have been varied to explore a large set of crystallization conditions and to correlate them with the thin film morphology. The latter has been characterized by a combined use of optical profilometry, polarized optical microscopy, X-ray reflectometry, and X-ray diffraction measurements. The characterization results confirm that the roughness and crystalline order of the thin films are improved after the temperature gradient treatments: (1) high cooling rate treatments (≥9 °C min-1) significantly reduce the roughness of high thickness films, leading to good continuity and uniformity of the films; (2) dendritic growth dominates not only the films with low thickness but also films with high thickness treated at low cooling rates (<9 °C min-1); (3) the out-of-plane order and the in-plane alignment of the crystallites are also remarkably enhanced by the temperature gradient treatments.