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On the inapplicability of electron-hopping models for the organic semiconductor Phenyl-C61-butyric Acid Methyl Ester (PCBM)

Journal Article · · Journal of Physical Chemistry Letters, 4(6):1012-1017
DOI:https://doi.org/10.1021/jz400227c· OSTI ID:1133236

Phenyl-C61-butyric Acid Methyl Ester (PCBM) is one of the most popular semiconductors in organic photovoltaic cells, but the electron transport mechanism in the microcrystalline domains of this material as well as its preferred packing structure remains unclear. Here we use density functional theory to calculate electronic coupling matrix elements, reorganization energies and activation energies for available experimental and model crystal structures. We find that the picture of an excess electron hopping from one fullerene to another does not apply for any of the crystalline phases, rendering traditional rate equations inappropriate. We also find that the cohesive energy increases in the order body-centred-cubic < hexagonal < simple cubic < monoclinic < triclinic, independently on the type of dispersion correction used. Our results indicate that the electron-ion dynamics needs to be solved explicitly in order to obtain a realistic description of charge transfer in this material. M.D. was supported by the U.S. Department of Energy (DOE), Office of Basic Energy Sciences (BES), Division of Chemical Sciences, Geosciences and Biosciences. PNNL is a multiprogram national laboratory operated for DOE by Battelle.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US)
Sponsoring Organization:
USDOE
DOE Contract Number:
AC05-76RL01830
OSTI ID:
1133236
Report Number(s):
PNNL-SA-94299; KC0301020
Journal Information:
Journal of Physical Chemistry Letters, 4(6):1012-1017, Journal Name: Journal of Physical Chemistry Letters, 4(6):1012-1017
Country of Publication:
United States
Language:
English

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