Three-dimensional anisotropic density of states distribution and intrinsic-like mobility in organic single crystals

Organic semiconducting molecules are receiving a large attention because of their potential applications, spanning from OLEDs to plastic photovoltaics to bio-chemical sensors. However, the electronic transport properties of these materials are still not fully understood, and organic single crystals (OSCs) may represent model materials for assessing the charge transport mechanisms, thanks to their high purity and molecular order. Here we show for the first time that solution-grown, millimiter-sized organic single crystals of 4-hydroxycyanobenzene (4HCB) possess a clear and reproducible three-dimensional anisotropy in their main transport parameters: (i) charge carrier mobility, (ii) distribution of the electronic density of states and (iii) deep traps energy and concentration, and we report intrinsic-like three-dimensional mobility values for these crystals. These findings demonstrate that the electronic spatial anisotropy of OSCs extends well beyond the carrier mobility, and open the way to the development of novel electronic device architectures based on the simultaneous exploitation of different electronic responses along the three spatial directions of the crystal.