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Issue 13, 2013
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Reassessing the use of one-electron energetics in the design and characterization of organic photovoltaics

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Abstract

We present results showing that common approximations employed in the design and characterization of organic photovoltaic (OPV) materials can lead to significant errors in widely adopted design rules. First, we assess the validity of the common practice of using HOMO and LUMO energies in place of formal redox potentials to characterize organic semiconductors. We trace the formal justification for this practice and survey its limits in a way that should be useful for those entering the field. We find that while the HOMO and LUMO energies represent useful descriptive approximations, they are too quantitatively inaccurate for predictive material design. Second, we show that the excitonic nature of common organic semiconductors makes it paramount to distinguish between the optical and electronic bandgaps for materials design. Our analysis shows that the usefulness of the “LUMO–LUMO Offset” as a design parameter for exciton dissociation is directly tied to the accuracy of the one-electron approximation. In particular, our results suggest that the use of the “LUMO–LUMO Offset” as a measure of the driving force for exciton dissociation leads to a systematic overestimation that should be cautiously avoided.

Graphical abstract: Reassessing the use of one-electron energetics in the design and characterization of organic photovoltaics

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Publication details

The article was received on 30 Jan 2013, accepted on 01 Feb 2013 and first published on 01 Feb 2013


Article type: Paper
DOI: 10.1039/C3CP50438G
Citation: Phys. Chem. Chem. Phys., 2013,15, 4538-4547
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    Reassessing the use of one-electron energetics in the design and characterization of organic photovoltaics

    B. M. Savoie, N. E. Jackson, T. J. Marks and M. A. Ratner, Phys. Chem. Chem. Phys., 2013, 15, 4538
    DOI: 10.1039/C3CP50438G

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