Unveiling the photophysics in solid-state organic materials: a study on BODIPY, porphyrin, and PBI based materials

Abstract

Organic semiconductors have applications in optoelectronics, light harvesting, and sensing as soft matter materials. One of the biggest challenges to overcome with organic-based materials is structural heterogeneity that arises from the self-assembly of monomers upon solid-state deposition. In this work we have investigated solid-state organic semiconductors with three levels of solution-phase processing: i) materials prepared from drop casting with no solution-phase processing on BODIPY systems ii) films prepared from pre-aggregation of the monomers with porphyrin systems iii) films prepared from aggregated monomers that were covalently stapled with perylene bisimide systems. In the BODIPY systems, we found that: i) the electronic states are highly coupled with a major redshift from 583 nm in the solution to 614 nm in the solid. ii) Through interpretation of the broadband transient absorption spectrum, the initial excited state is delocalized and localizes within the first 10 femtoseconds. iii) Using two color pump probe, we measured ultrafast diffusion at 14.37 + or - 2.79 cm 2 s -1 that abruptly halts after 10 ps. In the porphyrin systems with level 2 solution-phase processing, we have also shown that the lifetime of the excited state is correlated with the degree of structural order. The monomer exhibits the longest lifetime with an average lifetime of 1.26 ns, the aggregate is much shorter with a lifetime of 349 ps, and the films show substantially faster relaxation, with the film fabricated from the monomer having a 72.56 ps average lifetime, and the film composed of the aggregate having a 26 ps average lifetime. These results suggest that the lifetime decreases as the order and electronic coupling of the system increases, so much so that the lifetime is two orders of magnitude different. In the perylene bisimide systems, we did a direct spectroscopic comparison between thin films formed from noncovalent assemblies and from covalently tethered molecular assemblies. This indicates that interchromophore coupling is enhanced in the covalently tethered film. We saw a 73% increase in excited state transport compared to the control film, as well as a shorter and more homogenous excited state lifetime. Covalent tethering proves to be the best strategy for generating homogeneous materials.