A Kinetic Monte Carlo Study of Fullerene Adsorption within a Pc-PBBA Covalent Organic Framework and Implications for...

Two-dimensional covalent organic frameworks (COFs), with their predictable assembly into ordered porous crystalline materials, tunable composition, and high charge carrier mobility, offer the possibility of creating ordered bulk heterojunction solar cells given a suitable electron-transporting material to fill the pores. The photoconductive (hole-transporting) properties of many COFs have been reported, including the recent creation of a TT-COF/PCBM solar cell by Dogru et al. Although a prototype device has been fabricated, its poor solar efficiency suggests a potential issue with electron transport caused by the interior packing of the fullerenes. Such packing information is absent and cannot be obtained experimentally. In this paper, we use Kinetic Monte Carlo (KMC) simulations to understand the dominant pore-filling mechanisms and packing configurations of C60 molecules in a Pc-PBBA COF that are similar to the COF fabricated experimentally. The KMC simulations thus offer more realistic filling conditions than our previously used Monte Carlo (MC) techniques. We found persistently large separation distances between C60 molecules that are absent in the more tractable MC simulations and which are likely to hinder electron transport significantly. We attribute the looser fullerene packing to the existence of stable motifs with pairwise distances that are mismatched with the underlying adsorption lattice of the COF. We conclude that larger pore COFs may be necessary to optimize electron transport and hence produce higher efficiency devices.