Chain Conformation and Exciton Delocalization in a Push-Pull Conjugated Polymer.

Linear and nonlinear optical line shapes reveal details of excitonic structure in polymer semiconductors. We implement absorption, photoluminescence, and transient absorption spectroscopies in DPP-DTT, an electron push-pull copolymer, to explore the relationship between their spectral line shapes and chain conformation, deduced from resonance Raman spectroscopy and from ab initio calculations. The viscosity of precursor polymer solutions before film casting displays a transition that suggests gel formation above a critical concentration. Upon crossing this viscosity deflection concentration, the line shape analysis of the absorption spectra within a photophysical aggregate model reveals a gradual increase in interchain excitonic coupling. We also observe a red-shifted and line-narrowed steady-state photoluminescence spectrum along with increasing resonance Raman intensity in the stretching and torsional modes of the dithienothiophene unit, which suggests a longer exciton coherence length along the polymer-chain backbone. Furthermore, we observe a change of line shape in the photoinduced absorption component of the transient absorption spectrum. The derivative-like line shape may originate from two possibilities: a new excited-state absorption or Stark effect, both of which are consistent with the emergence of a high-energy shoulder as seen in both photoluminescence and absorption spectra. Therefore, we conclude that the exciton is more dispersed along the polymer chain backbone with increasing concentrations, leading to the hypothesis that polymer chain order is enhanced when the push-pull polymers are processed at higher concentrations. Thus, tuning the microscopic chain conformation by concentration would be another factor of interest when considering the polymer assembly pathways for pursuing large-area and high-performance organic optoelectronic devices.