The novel technique based on air-gap transistor stamps enabled realization of the intrinsic (not dominated by static disorder) transport of the electric-field-induced charge carriers on the surface of rubrene crystals over a wide temperature range. The signatures of the intrinsic transport are the anisotropy of the carrier mobility, µ, and the growth of µ with cooling. The anisotropy of µ vanishes in the activation regime at lower temperatures, where the charge transport becomes dominated by shallow traps. The deep traps, deliberately introduced into the crystal by X-ray radiation, increase the field-effect threshold without affecting the mobility. These traps filled above the field-effect threshold do not scatter the mobile polaronic carriers.

We introduce a method to fabricate high-performance field-effect transistors on the surface of freestanding organic single crystals. The transistors are constructed by laminating a monolithic elastomeric transistor stamp against the surface of a crystal. This method, which eliminates exposure of the fragile organic surface to the hazards of conventional processing, enables fabrication of rubrene transistors with charge carrier mobilities as high as approximately 15 cm2/V.s and subthreshold slopes as low as 2nF.V/decade.cm2. Multiple relamination of the transistor stamp against the same crystal does not affect the transistor characteristics; we exploit this reversibility to reveal anisotropic charge transport at the basal plane of rubrene.

We have observed the Hall effect in the field-induced accumulation layer on the surface of single-crystal samples of a small-molecule organic semiconductor rubrene. The Hall mobility muH increases with decreasing temperature in both the intrinsic (high-temperature) and trap-dominated (low-temperature) conduction regimes. In the intrinsic regime, the density of mobile field-induced charge carriers extracted from the Hall measurements, nH, coincides with the density n calculated using the gate-channel capacitance and becomes smaller than n in the trap-dominated regime. The Hall data are consistent with the diffusive bandlike motion of field-induced charge carriers between trapping events.

Small-molecule organic semiconductors, together with polymers, form the basis for the emerging field of organic electronics. Despite the rapid technological progress in this area, our understanding of fundamental electronic properties of these materials remains limited. Recently developed organic field-effect transistors ͑OFETs͒ based on single crystals of small-molecule organic materials are characterized by an unprecedented quality and reproducibility. These devices provide a unique tool to study the fundamentals of polaronic transport on organic surfaces and to explore the limits of OFET performance. This Colloquium focuses on the intrinsic, not limited by static disorder, charge transport in single-crystal OFETs and on the nature of defects on surfaces of organic crystals. In the conclusion, an outline of the outstanding problems that are now becoming within experimental reach owing to the development of single-crystal OFETs is presented.

We present an overview of recent studies of the charge transport in the field effect transistors on the surface of single crystals of organic low-molecular-weight materials. We first discuss in detail the technological progress that has made these investigations possible. Particular attention is devoted to the growth and characterization of single crystals of organic materials and to different techniques that have been developed for device fabrication. We then concentrate on the measurements of the electrical characteristics. In most cases, these characteristics are highly reproducible and demonstrate the quality of the single crystal transistors. Particularly noticeable are the small sub-threshold slope, the non-monotonic temperature dependence of the mobility, and its weak dependence on the gate voltage. In the best rubrene transistors, room-temperature values of m as high as 15 cm 2 /Vs have been observed. This represents an order-of-magnitude increase with respect to the highest mobility previously reported for organic thin film transistors. In addition, the highest-quality single-crystal devices exhibit a significant anisotropy of the conduction properties with respect to the crystallographic direction. These observations indicate that the field effect transistors fabricated on single crystals are suitable for the study of the intrinsic electronic properties of organic molecular semiconductors. We conclude by indicating some directions in which near-future work should focus to progress further in this rapidly evolving area of research.