Journal
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 13, Issue 2, Pages 544-551Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.1c03901
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Funding
- China Postdoctoral Science Foundation [2019M662911]
- National Natural Science Foundation of China [62004069, 51521002]
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The power conversion efficiency of organic photovoltaics is limited by the disordered nature of organic semiconductors. The emission line-shape in organic semiconductors is associated with a state-filling effect and can indicate the energetic disorder. Molecular geometry plays a crucial role in narrowing the energetic distribution and facilitating larger electron delocalization.
The power conversion efficiency of organic photovoltaics is strongly limited by relatively large energy loss, which is partially due to the disordered nature of organic semiconductors. This disordered nature not only hinders the rational design of molecules with excellent photophysical properties but also prevents a more thorough understanding of the inherent link between microscopic parameters and physical phenomena. In this Perspective, we demonstrate that the injection-dependent emission line-shape in organic semiconductors is primarily associated with a state-filling effect, where the extent of spectral blue-shift can be a strong indicator for energetic disorder. Molecular geometry with rigidity and coplanarity not only promotes preferential faceon stacking that narrows the energetic distribution of subgap states but also impedes torsional deformations of the conjugated backbone away from planarity, thereby facilitating larger pi-electron delocalization. These structural characteristics explain the seemingly contradictory high radiative efficiency of low-bandgap nonfullerene molecules, providing promising molecular design strategies to realize high-efficiency organic photovoltaics.
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