Prediction of Band Mobilities of Pentacene, Rubrene and C₈-BTBT from First Principle Calculations

Design, synthesis, chemical stability, packing, cyclic voltammetry, ionisation potential, and charge transport of [1]benzothieno[3,2-b][1]benzothiophene derivatives

“…In order to probe whether the lower hole mobility measured for 2a has an intrinsic origin or is only due to a less uniform packing, as suggested by POM images, the hole transport properties of 1a and 2a have been investigated at the theoretical level, considering in the first approximation a hopping transport regime (see Experimental section). The internal reorganization energies associated to positive polarons are larger for 2a (360 meV and 245 meV for 2a and 1a, respectively, in agreement with earlier studies) 71,72 and hence detrimental for hole transport. This evolution is consistent with a previous work pointing to a systematic increase in the reorganization energies of discotic conjugated compounds upon introduction of oxygen atoms between the conjugated core and alkyl chains.…”

“…The order of magnitude of the calculated hole mobilities are consistent with the measured mobilities as well as with previous theoretical data obtained in the hopping regime limit. 71 Note also that higher hole mobilities have been reported for 1a (~36 cm²/Vs) 72 when considering a band model, as expected. In light of the results provided by the two extreme theoretical models, the experimental mobilities suggest that charge transport occurs rather through a hopping regime than a band regime hindered by the presence of structural defects since POM images reveal large crystals.…”

Quantitative analysis of intermolecular interactions in orthorhombic rubrene

“…Furthermore, the confirmation of Á Á Á interactions from the NCI analysis correlate well with the topological properties obtained by the QTAIM analysis. Additionally, it supports earlier theoretical predictions (Wen et al, 2009;Kobayashi et al, 2013;Stehr et al, 2011) and single-crystal FET characteristics (Podzorov et al, 2004), where an anisotropic charge transfer was observed for rubrene with the highest charge mobility along the crystallographic b axis due to the stacking interactions between the tetracene backbones. RDG isosurfaces for the C4Á Á ÁH5 interaction are highlighted in Fig.…”

Molecular Semiconductors for Logic Operations: Dead‐End or Bright Future?

“…For example, data for pentacene 1 afford I exp = 1.29, I band = 1.76, and I hop = 1.09. Some differences are also observed with rubrene 3 I exp = 1.25, I band = 1.35, and I hop = 1.00 . For DNTT 9 ( R = H), I exp ranges from 1.59 to 1.76 .…”