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We have adapted the microscopic theory of nucleation for the epitaxial growth of inorganic materials to the nucleation of organic small molecules on an inert substrate like the gate dielectric of an organic thin-film transistor. The parameters required to explore the model were calculated with the standard MM3 force field and also include experimentally determined vapor pressure data, as well as film growth data. Sufficient agreement is found between the experimentally determined equilibrium crystal shape and heats of sublimation on the one hand and the calculated parameters on the other hand. The growth of pentacene, tetracene, and perylene on inert substrates has been studied in terms of this theory, especially focusing on the two-dimensional ͑2D͒ to 3D nucleation transition. It is demonstrated that 3D nucleation leads to ill-connected grains, while 2D nucleated grains form continuous films suitable for charge transport. The analysis of this transition allows for the experimental determination of the molecule-substrate interactions for a given molecule on a given surface. It was found that the deposition conditions for 2D growth shift to less favorable substrate temperatures and deposition rates as the difference between interlayer interactions and molecule-substrate interactions increase and the intralayer interactions decrease. Moreover, those interactions affect the nucleation rate and therefore the ultimate 2D grain size that can be obtained.

The properties of the dielectric strongly influence the performance of organic thin-film transistors. In this letter, we show experimental results that quantify the influence of the roughness of the dielectric on the mobility of pentacene transistors and discuss the cause of it. We consider the movement of charge carriers out of the "roughness valleys" or across those valleys at the dielectricsemiconductor interface as the limiting step for the roughness-dependent mobility in the transistor channel.

Organic semiconductors are characterized by localized states whose energies are predominantly determined by electrostatic interactions with their immediate molecular environment. As a result, the details of the energy landscape at heterojunctions between different organic semiconductors cannot simply be deduced from those of the individual semiconductors, and they have so far remained largely unexplored. Here, microelectrostatic computations are performed to clarify the nature of the electronic structure and geminate pair energetics at the pentacene/C60 interface, as archetype for an interface between a donor molecule and a fullerene electron acceptor. The size and orientation of the molecular quadrupole moments, determined by material choice, crystal orientation, and thermodynamic growth parameters of the semiconductors, dominate the interface energetics. Not only do quadrupoles produce direct electrostatic interactions with charge carriers, but, in addition, the discontinuity of the quadrupole field at the interface induces permanent interface dipoles. That discontinuity is particularly striking for an interface with C60 molecules, which by virtue of their symmetry possess no quadrupole. Consequently, at a pentacene/C60 interface, both the vacuum‐level shift and geminate pair dissociation critically depend on the orientation of the pentacene π‐system relative to the adjacent C60.

We derive an analytical formula for the open-circuit voltage ͑V oc ͒ of organic planar heterojunction solar cells under standard operating conditions. We find that the type of free carrier recombination at the interface between the donor and acceptor materials controls the slope of V oc vs incident light intensity. By using the same derivation, an equation for the resistance around V oc is obtained. From this, we investigate two parameters in more detail and compare them to experiments. The first is the work function of the cathode metal. We show that, within our model, V oc does not depend on this work function, while the cell resistance around V oc is strongly dependent on it. Second, we find that the asymptotic resistance around V oc is a third-order power function of the thickness of the organic layers ͑acceptor or donor͒. The model provides insights to achieve low-resistivity high open-circuit voltage organic solar cells.

The electronic structure at organic/organic interfaces plays a key role, among others, in defining the quantum efficiency of organics-based photovoltaic cells. Here, we perform quantum-chemical and microelectrostatic calculations on molecular aggregates of various sizes and shapes to characterize the interfacial dipole moment at pentacene/C 60 heterojunctions. The results show that the interfacial dipole mostly originates in polarization effects due to the asymmetry in the multipolar expansion of the electronic density distribution between the interacting molecules, rather than in a charge transfer from donor to acceptor. The local dipole is found to fluctuate in sign and magnitude over the interface and appears as a sensitive probe of the relative arrangements of the pentacene and C 60 molecules (and of the resulting local electrical fields sensed by the molecular units).

The mechanism by which molecular dopants donate free charge carriers to the host organic semiconductor is investigated and is found to be quite different from the one in inorganic semiconductors. In organics, a strong correlation between the doping concentration and its charge donation efficiency is demonstrated. Moreover, there is a threshold doping level below which doping simply has no electrical effect.

Grain boundaries are the most inevitable and pronounced structural defects in pentacene films. To study the effect of those structural defects on the electronic state distribution, the energy levels of a hole on molecules at and near the defect have been calculated using a submolecular self-consistent-polarization-field approach in combination with atomic charge-quadrupole interaction energy calculations. This method has been benchmarked prior to application on four idealized grain boundaries: a grain boundary void, a void with molecules squeezed in between two grains, a boundary between two grains with different crystallographic orientations, and a grain boundary void in which a permanent dipole ͑e.g., a water molecule͒ has nested. While idealized, those views highlight different aspects of real grain boundaries. Implications on macroscopic charge transport models are discussed, as well as some relation between growth conditions and the formation of the grain boundary.