Acenes have long been the subject of intense study because of the unique electronic properties associated with their pi-bond topology. Recent reports of impressive semiconductor properties of larger homologues have reinvigorated research in this field, leading to new methods for their synthesis, functionalization, and purification, as well as for fabricating organic electronic components. Studies performed on high-purity acene single crystals revealed their intrinsic electronic properties and provide useful benchmarks for thin film device research. New approaches to add functionality were developed to improve the processability of these materials in solution. These new functionalization strategies have recently allowed the synthesis of acenes larger than pentacene, which have hitherto been largely unavailable and poorly studied, as well as investigation of their associated structure/property relationships.

The larger acenes: versatile organic semiconductors.

Tetrathiafulvalenes, oligoacenenes, and their buckminsterfullerene derivatives: the brick and mortar of organic electronics.

The past couple of years have witnessed a remarkable burst in the development of organic field-effect transistors (OFETs), with a number of organic semiconductors surpassing the benchmark mobility of 10 cm2/(V s). In this perspective, we highlight some of the major milestones along the way to provide a historical view of OFET development, introduce the integrated molecular design concepts and process engineering approaches that lead to the current success, and identify the challenges ahead to make OFETs applicable in real applications.

Integrated materials design of organic semiconductors for field-effect transistors

We have obtained a hole mobility for the organic conductor pentacene of μ=35 cm2/V s at room temperature increasing to μ=58 cm2/V s at 225 K. These high mobilities result from a purification process in which 6,13-pentacenequinone was removed by vacuum sublimation. The number of traps is reduced by two orders of magnitude compared with conventional methods. The temperature dependence of the mobility is consistent with the band model for electronic transport.

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Effect of impurities on the mobility of single crystal pentacene

Theoretical investigations of charge transport in organic materials are generally based on the "energy splitting in dimer" method and routinely assume that the transport parameters (site energies and transfer integrals) determined from monomer and dimer calculations can be reliably used to describe extended systems. Here, we demonstrate that this transferability can fail even in molecular crystals with weak van der Waals intermolecular interactions, due to the substantial (but often ignored) impact of polarization effects, particularly on the site energies. We show that the neglect of electronic polarization leads to qualitatively incorrect values and trends for the transfer integrals computed with the energy splitting method, even in simple prototypes such as ethylene or pentacene dimers. The polarization effect in these systems is largely electrostatic in nature and can change dramatically upon transition from a dimer to an extended system. For example, the difference in site energy for a prototypical "face-to-edge" one-dimensional stack of pentacene molecules is calculated to be 30% greater than that in the "face-to-edge" dimer, whereas the site energy difference in the pentacene crystal is vanishingly small. Importantly, when computed directly in the framework of localized monomer orbitals, the transfer integral values for dimer and extended systems are very similar.

Effect of electronic polarization on charge-transport parameters in molecular organic semiconductors.

Pentacene, C22H14, crystallizes in different morphologies characterized by their d(001)-spacings of 14.1, 14.5, 15.0 and 15.4 A. We have studied the crystal structure of the 14.1 and 14.5 A d-spacing morphologies grown by vapour transport and from solution. We find a close correspondence between the 14.1 A structure reported by Holmes, Kumaraswamy, Matzeger & Vollhardt [Chem. Eur. J. (1999), 5, 3399–3412] and the 14.5 A structure reported by Campbell, Monteath Robertson & Trotter [Acta Cryst. (1961), 14, 705–711]. Single crystals commonly adopt the 14.1 A d-spacing morphology with an inversion centre on both mol­ecules in the unit cell. Thin films grown on SiO2 substrates above 350 K preferentially adopt the 14.5 A d-spacing morphology, with a slightly smaller unit-cell volume.

Polymorphism in pentacene

Identification of polymorphs of pentacene

Pentacene crystallizes in a layered structure with a herringbone arrangement within the layers. The electronic properties depend strongly on the stacking of the molecules within the layers (Haddon et al., 2002). We have synthesized four different polymorphs of pentacene, identified by their layer periodicity, d(001): 14.1, 14.4, 15.0 and 15.4 A. Single crystals commonly adopt the 14.1 A structure, whereas all four polymorphs can be synthesized in thin film form, depending on growth conditions. We have identified part of the unit cell parameters of these polymorphs by X-ray and electron diffraction. The 15.0 and 15.4 A polymorphs transform at elevated temperature to the 14.1 and 14.4 A polymorphs, respectively. Using SCLC measurements, we determined the mobility of the 14.1 A polymorph to be 0.2 cm^2/Vs at room temperature.

Anne B. Dros

Papers

Polymorphism in pentacene

Identification of polymorphs of pentacene

Identification of polymorphs of pentacene

Polymorphism in Pentacene.