In organic field-effect transistors (FETs), charges move near the surface of an organic semiconductor, at the interface with a dielectric. In the past, the nature of the microscopic motion of charge carriers--which determines the device performance--has been related to the quality of the organic semiconductor. Recently, it was discovered that the nearby dielectric also has an unexpectedly strong influence. The mechanisms responsible for this influence are not understood. To investigate these mechanisms, we have studied transport through organic single-crystal FETs with different gate insulators. We find that the temperature dependence of the mobility evolves from metallic-like to insulating-like with increasing dielectric constant of the insulator. The phenomenon is accounted for by a two-dimensional Fröhlich polaron model that quantitatively describes our observations and shows that increasing the dielectric polarizability results in a crossover from the weak to the strong polaronic coupling regime. This represents a considerable step forward in our understanding of transport through organic transistors, and identifies a microscopic physical process with a large influence on device performance.

Charge transport in crystalline organic semiconductors is intrinsically limited by the presence of large thermal molecular motions, which are a direct consequence of the weak van der Waals inter-molecular interactions. These lead to an original regime of transport called transient localization, sharing features of both localized and itinerant electron systems. After a brief review of experimental observations that pose a challenge to the theory, we concentrate on a commonly studied model which describes the interaction of the charge carriers with inter-molecular vibrations. We present different theoretical approaches that have been applied to the problem in the past, and then turn to more modern approaches that are able to capture the key microscopic phenomenon at the origin of the puzzling experimental observations, i.e. the quantum localization of the electronic wavefuntion at timescales shorter than the typical molecular motions. We describe in particular a relaxation time approximation which clarifies how the transient localization due to dynamical molecular motions relates to the Anderson localization realized for static disorder, and allows us to devise strategies to improve the mobility of actual compounds. The relevance of the transient localization scenario to other classes of systems is briefly discussed.

The charge mobility of molecular semiconductors is limited by the large fluctuation of intermolecular transfer integrals, often referred to as off-diagonal dynamic disorder, which causes transient localization of the carriers' eigenstates. Using a recently developed theoretical framework, we show here that the electronic structure of the molecular crystals determines its sensitivity to intermolecular fluctuations. We build a map of the transient localization lengths of high-mobility molecular semiconductors to identify what patterns of nearest-neighbour transfer integrals in the two-dimensional (2D) high-mobility plane protect the semiconductor from the effect of dynamic disorder and yield larger mobility. Such a map helps rationalizing the transport properties of the whole family of molecular semiconductors and is also used to demonstrate why common textbook approaches fail in describing this important class of materials. These results can be used to rapidly screen many compounds and design new ones with optimal transport characteristics.

We analyze a model that accounts for the inherently large thermal lattice fluctuations associated with the weak van der Waals intermolecular bonding in crystalline organic semiconductors. In these materials the charge mobility generally exhibits a "metalliclike" power-law behavior, with no sign of thermally activated hopping characteristic of carrier self-localization, despite apparent mean free paths comparable to or lower than the intermolecular spacing. Our results show that such a puzzling transport regime can be understood from the simultaneous presence of band carriers and incoherent states that are dynamically localized by the thermal lattice disorder.

A dynamical mean-field theory of the small polaron problem is presented, which becomes exact in the limit of infinite dimensions. The ground state properties and the one-electron spectral function are obtained for a single electron interacting with Einstein phonons by a mapping of the lattice problem onto a polaronic impurity model. The one-electron propagator of the impurity model is calculated through a continued fraction expansion (CFE), both at zero and finite temperature, for any electron-phonon coupling and phonon energy. In contrast to the ground state properties such as the effective polaron mass, which have a smooth behaviour, spectral properties exhibit a sharp qualitative change at low enough phonon frequency: beyond a critical coupling, one energy gap and then more and more open in the density of states at low energy, while the high energy part of the spectrum is broad and can be explained by a strong coupling adiabatic approximation. As a consequence narrow and coherent low-energy subbands coexist with an incoherent featureless structure at high energy. The subbands denote the formation of quasiparticle polaron states. Also, divergencies of the self-energy may occur in the gaps. At finite temperature such effect triggers an important damping and broadening of the polaron subbands. On the other hand, in the large phonon frequency regime such a separation of energy scales does not exist and the spectrum has always a multipeaked structure.Comment: 21 Pages Latex, 19 PostScript figure