Effect of Alkyl Chain Length on Charge Transport Property of Anthracene-Based Organic Semiconductors.

Abstract

Anthracene, a simple planar building block for organic semiconductors, shows strong intermolecular interactions and exhibits strong blue fluorescence. Thus, its derivatives have a great potential to integrate considerable charge carrier mobility and strong emission within a molecule. Here, we systematically studied the influence of alkyl chain length on the crystal structures, thermal properties, photophysical characteristics, electrochemical behaviors, and mobilities for a series of 2,6-di(4-alkyl-phenyl)anthracenes (Cn-Ph-Ants, where n represents the alkyl chain length). Among them, Cn-Ph-Ants (n = 0, 1, 2, and 3) display similar layered herringbone (LHB) packing motifs, which facilitate two-dimensional charge transport and thereby enables high-performance organic field-effect transistors (OFETs). All Cn-Ph-Ants exhibit similar work functions and show strong blue fluorescence with photoluminescence quantum yields (PLQY) of approximately 40% in toluene. In addition, the absolute powder PLQYs of C0-, C2-, C3-, C4-, and C6-Ph-Ants are 24.6, 8.2, 5.7, 10.9, and 8.6%, respectively. Note that the alkyl chain length shows a significant effect on the charge mobilities of Cn-Ph-Ants. Our newly synthesized C1-, C3-, and C4-Ph-Ants show hole mobilities of up to 2.40, 1.34, and 1.00 cm2 V-1 s-1, respectively, with mobilities of 3.40, 1.57, and 0.82 cm2 V-1 s-1 for C0-, C2-, and C6-Ph-Ants, indicating an increasing tendency of mobility with shorter alkyl chain length. This feature is related to the microstructures of the thin films, which reveal the enhanced film order, crystallinity, and grain size with a decrease in the alkyl chain length. Moreover, we theoretically analyze the intermolecular transfer integrals of HOMOs, which increase at T-shaped contacts as the alkyl chain length decreases, which improves the intermolecular charge transport properties, leading to the increases in mobility. Interestingly, the anisotropy of the transfer integral tends to decrease upon substitution with longer alkyl chains, suggesting that alkyl chain adjustments may facilitate isotropic charge transport property in 2,6-alkylated anthracenes.