The formation of donor–acceptor complexes (DACs) between the electron donor Dibenzotetrathiafulvalene (DBTTF) and the acceptor Hexaazatriphenylenehexacarbonitrile (HATCN) results in a separated phase with a distinctly different crystal structure as well as optical absorption bands below the energy gaps of the two pristine materials. X-ray scattering and atomic force microscopy provide detailed insights into the film structure and morphology by systematic variation of the mixing ratio from pristine DBTTF to pristine HATCN. The measured electrical conductivity of thin films depends in a highly nonmonotonic manner on the composition of the mixture and shows significantly improved charge transport compared to the pristine films. The temperature-dependent conductivity, charge carrier concentration, and mobility were investigated across these compositions. Surprisingly, all compositions exhibited n-type behavior, except for pristine DBTTF. This behavior is explained by the electronic structure of the mixtures, as revealed by ultraviolet photoelectron spectroscopy, which indicates that charge injection and transport occur via the lowest unoccupied molecular orbital of the DAC and HATCN. Additionally, the observed electrical conductivity is strongly influenced by the morphology and structural ordering of the films. These findings offer valuable insights for the design of advanced materials with enhanced electrical performance.
Opitz et al. (2026) studied this question.