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Optoelectronic devices based on conjugated polymers often rely on multilayer device architectures, as it is difficult to design all the different functional requirements, in particular the need for efficient luminescence and fast carrier transport, into a single polymer. Here we study the photophysics of a recently discovered class of conjugated polymers with high charge carrier mobility and low degree of energetic disorder and investigate whether it is possible in this system to achieve by molecular design a high photoluminescence quantum yield without sacrificing carrier mobility. Tracing exciton dynamics over femtosecond to microsecond time scales, we show that nearly all nonradiative exciton recombination arises from interactions between chromophores on different chains. We evaluate the temperature dependence and role of electron-phonon coupling leading to fast internal conversion in systems with strong interchain coupling and the extent to which this can be turned off by varying side chain substitution. By sterically decreasing interchain interaction, we present an effective approach to increase the fluorescence quantum yield of low-energy gap polymers. We present a red-NIR-emitting amorphous polymer with the highest reported film luminescence quantum efficiency of 18% whose mobility concurrently exceeds that of amorphous-Si. This is a key result toward the development of single-layer optoelectronic devices that require both properties.

Many optoelectronic devices based on organic materials require rapid and long-range singlet exciton transport. Key factors controlling exciton transport include material structure, exciton–phonon coupling and electronic state symmetry. Here, we employ femtosecond transient absorption microscopy to study the influence of these parameters on exciton transport in one-dimensional conjugated polymers. We find that excitons with 21Ag– symmetry and a planar backbone exhibit a significantly higher diffusion coefficient (34 ± 10 cm2 s–1) compared to excitons with 11Bu+ symmetry (7 ± 6 cm2 s–1) with a twisted backbone. We also find that exciton transport in the 21Ag– state occurs without exciton–exciton annihilation. Both 21Ag– and 11Bu+ states are found to exhibit subdiffusive behavior. Ab initio GW-BSE calculations reveal that this is due to the comparable strengths of the exciton–phonon interaction and exciton coupling. Our results demonstrate the link between electronic state symmetry, backbone torsion and phonons in exciton transport in π-conjugated polymers.

We introduce femtosecond wide-field transient absorption microscopy combining sub-10 fs pump and probe pulses covering the complete visible (500–650 nm) and near-infrared (650–950 nm) spectrum with diffraction-limited optical resolution. We demonstrate the capabilities of our system by reporting the spatially- and spectrally-resolved transient electronic response of MAPbI3–xClx perovskite films and reveal significant quenching of the transient bleach signal at grain boundaries. The unprecedented temporal resolution enables us to directly observe the formation of band-gap renormalization, completed in 25 fs after photoexcitation. In addition, we acquire hyperspectral Raman maps of TIPS pentacene films with sub-400 nm spatial and sub-15 cm–1 spectral resolution covering the 100–2000 cm–1 window. Our approach opens up the possibility of studying ultrafast dynamics on nanometer length and femtosecond time scales in a variety of two-dimensional and nanoscopic systems.