Organic semiconductors are already widely used in electronics. Nevertheless, their fundamental properties are still being debated. In particular, charge transport, which determines the performance of organic light-emitting diodes, solar cells and organic field-effect transistors, has been described by a wide range of complementary but incompatible theories. These theories involve either localized charge carriers hopping from molecule to molecule, leading to incoherent charge transport, or delocalized charge carriers moving around freely in the semiconductor, leading to coherent transport. In this communication, we reveal the first experimental evidence that charge coherence can be tuned from partially to fully coherent in one and the same material -pentacene-showing a continuous transition from one transport mechanism to the other. Microscopically, the transport mechanism depends on the overlap of adjacent molecular orbitals, which in turn is sensitive to molecular thermal fluctuations. We control these fluctuations through moderate variations of pressure and temperature, leading to a mobility increase of 75%. We quantify the influence of these thermal fluctuations by estimating the critical value below which fully coherent charge transport emerges. The ability to control thermal fluctuations and therefore to effectively tune the charge coherence is an important key to improving charge transport in soft molecular materials.
INTRODUCTIONHistorically, the existence of coherent electronic states in weakly van der Waals bonded crystals has been a controversial topic. 1 The weak intermolecular interaction leads to a strong thermal vibration of each molecule, resulting in the dynamic disorder of the crystal lattice. Dynamic disorder subsequently leads to a complex interaction between the soft lattice and the charge carriers, which is unique to these systems. In classical semiconductors, the charge transport mechanism can be directly determined from the temperature dependence of the mobility. In an organic semiconductor, however, the temperature dependence of the mobility does not necessarily reveal the nature of the charge transport and therefore it cannot be determined whether a system is described by the short-range hopping of localized charge carriers or band transport due to extended electronic wavefunctions. 2 For this reason, a more direct method is required to study the nature of charge transport in these systems. The Hall effect is such a method, as it is directly connected to the coherence of the charge carrier wavefunction via interaction with the applied magnetic field. The quantum mechanical origin of this interaction lies in the coupling of the wave number k of the delocalized charge carrier wavefunction with the vector potential A of the magnetic field.