Chiral molecules exist as pairs of nonsuperimposable mirror images; a fundamental symmetry property vastly underexplored in organic electronic devices. Here, we show that organic field-effect transistors (OFETs) made from the helically chiral molecule 1-aza[6]helicene can display up to an 80-fold difference in hole mobility, together with differences in thin-film photophysics and morphology, solely depending on whether a single handedness or a 1:1 mixture of left- and right-handed molecules is employed under analogous fabrication conditions. As the molecular properties of either mirror image isomer are identical, these changes must be a result of the different bulk packing induced by chiral composition. Such underlying structures are investigated using crystal structure prediction, a computational methodology rarely applied to molecular materials, and linked to the difference in charge transport. These results illustrate that chirality may be used as a key tuning parameter in future device applications
The potential of a given π-conjugated organic molecule in an organic semiconductor device is highly dependent on molecular packing, as it strongly influences the charge-carrier mobility of the material. Such solid-state packing is sensitive to subtle differences in their intermolecular interactions and is challenging to predict. Chirality of the organic molecule adds an additional element of complexity to intuitive packing prediction. Here we use crystal structure prediction to explore the lattice-energy landscape of a potential chiral organic semiconductor, [6]helicene. We reproduce the experimentally observed enantiopure crystal structure and explain the absence of an experimentally observed racemate structure. By exploring how the hole and electron-mobility varies across the energy-structure-function landscape for [6]helicene, we find that an energetically favourable and frequently occurring packing motif is particularly promising for electron-mobility, with a highest calculated mobility of 2.9 cm V s (assuming a reorganization energy of 0.46 eV). We also calculate relatively high hole-mobility in some structures, with a highest calculated mobility of 2.0 cm V s found for chains of helicenes packed in a herringbone fashion. Neither the energetically favourable nor high charge-carrier mobility packing motifs are intuitively obvious, and this demonstrates the utility of our approach to computationally explore the energy-structure-function landscape for organic semiconductors. Our work demonstrates a route for the use of computational simulations to aid in the design of new molecules for organic electronics, through the a priori prediction of their likely solid-state form and properties.
The photochemistry and stability of fullerene films is found to be strongly dependent upon film nanomorphology. In particular, PCBM blend films, dispersed with polystyrene, are found to be more susceptible to photobleaching in air than the more aggregated neat films. This enhanced photobleaching correlated with increased oxygen quenching of PCBM triplet states and the appearance of a carbonyl FTIR absorption band indicative of fullerene oxidation, suggesting PCBM photo-oxidation is primarily due to triplet-mediated singlet oxygen generation. PCBM films were observed to undergo photo-oxidation in air for even modest (≤40 min) irradiation times, degrading electron mobility substantially, indicative of electron trap formation. This conclusion is supported by observation of red shifts in photo- and electro-luminescence with photo-oxidation, shown to be in agreement with time-dependent density functional theory calculations of defect generation. These results provide important implications on the environmental stability of PCBM-based films and devices.
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