Acceptor Energy Offset Manages Ultrafast Recombination Dynamics in Donor-Acceptor Mixtures

We study charge recombination rates in blends of MEH-PPV and a comprehensive set of low molecular-weight fluorine-based acceptors, using visible-pump – IR-probe photoinduced absorption technique. The positions of acceptor’s HOMO-LUMO levels are engineered by addition of different chemical substituents. The results clearly show the exponential scaling of the charge recombination rate with the acceptor LUMO energy. The minimal donor-acceptor LUMO energy difference required to form a CTC state is estimated as ~0.25 eV.

Charge Transfer Dynamics in Donor-Acceptor Complexes between a Conjugated Polymer and Fluorene Acceptors

We report on ground and excited state charge transfer in charge-transfer complexes in films formed between a semiconducting polymer, MEH-PPV (poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene]), and a series of fluorene electron acceptors. The latter were designed to vary systematically the electron affinity (EA) over 1.5 eV by attachment of various electron withdrawing groups to the fluorene core. The EAs of the acceptors are determined by cyclic voltammetry and compared with those from density functional theory calculations. The charge-transfer dynamics are studied using an ultrafast visible-pumpIR-probe photoinduced absorption technique. We demonstrate that the acceptor EA is the keybut not the onlyparameter that governs charge recombination rates that scale exponentially with the acceptor EA. From the time-resolved data we deduced a model that describes charge dynamics for acceptors with low and high EAs. The two opposite trendshigher acceptor EA increases the driving force for charge separation but also inevitably increases the rate of undesirable charge recombinationshould be carefully counterbalanced in designing novel polymerfullerene bulk heterojunctions

Acceptor Energy Offset Manages Ultrafast Recombination Dynamics in Donor-Acceptor Mixtures

We study charge recombination rates in blends of MEH-PPV and a comprehensive set of low molecular-weight fluorine-based acceptors, using visible-pump – IR-probe photoinduced absorption technique. The positions of acceptor’s HOMO-LUMO levels are engineered by addition of different chemical substituents. The results clearly show the exponential scaling of the charge recombination rate with the acceptor LUMO energy. The minimal donor-acceptor LUMO energy difference required to form a CTC state is estimated as ~0.25 eV