Defect healing at room temperature in pentacene thin films and improved transistor performance

We report on a healing of defects at room temperature in the organic semiconductor pentacene. This peculiar effect is a direct consequence of the weak intermolecular interaction which is characteristic of organic semiconductors. Pentacene thin-film transistors were fabricated and characterized by in situ gated four-terminal measurements. Under high vacuum conditions (base pressure of order 10E-8 mbar), the device performance is found to improve with time. The effective field-effect mobility increases by as much as a factor of two and mobilities up to 0.45 cm2/Vs were achieved. In addition, the contact resistance decreases by more than an order of magnitude and there is a significant reduction in current hysteresis. Oxygen/nitrogen exposure and annealing experiments show the improvement of the electronic parameters to be driven by a thermally promoted process and not by chemical doping. In order to extract the spectral density of trap states from the transistor characteristics, we have implemented a powerful scheme which allows for a calculation of the trap densities with high accuracy in a straightforward fashion. We show the performance improvement to be due to a reduction in the density of shallow traps <0.15 eV from the valence band edge, while the energetically deeper traps are essentially unaffected. This work contributes to an understanding of the shallow traps in organic semiconductors and identifies structural point defects within the grains of the polycrystalline thin films as a major cause.Comment: 13 pages, 13 figures, to be published in Phys. Rev.

Photoelectron spectra in an autoionization system interacting with a neighboring atom

Photoelectron ionization spectra of an autoionization system with one discrete level interacting with a neighbor two-level atom are discussed. The formula for long-time ionization spectra is derived. According to this formula, the spectra can be composed of up to eight peaks. Moreover, the Fano-like zeros for weak optical pumping have been identified in these spectra. The conditional ionization spectra depending on the state of the neighbor atom exhibit oscillations at the Rabi frequency. Dynamical spectral zeros occurring once per the Rabi period have been revealed in these spectra.Comment: 10 pages, 13 figure

Non conventional screening of the Coulomb interaction in low dimensional and finite size system

We study the screening of the Coulomb interaction in non polar systems by polarizable atoms. We show that in low dimensions and small finite size systems this screening deviates strongly from that conventionally assumed. In fact in one dimension the short range interaction is strongly screened and the long range interaction is anti-screened thereby strongly reducing the gradient of the Coulomb interaction and therefore the correlation effects. We argue that this effect explains the success of mean field single particle theories for large molecules.Comment: 4 pages, 5 figure

Light Quasiparticles Dominate Electronic Transport in Molecular Crystal Field-Effect Transistors

We report on an infrared spectroscopy study of mobile holes in the accumulation layer of organic field-effect transistors based on rubrene single crystals. Our data indicate that both transport and infrared properties of these transistors at room temperature are governed by light quasiparticles in molecular orbital bands with the effective masses m* comparable to free electron mass. Furthermore, the m* values inferred from our experiments are in agreement with those determined from band structure calculations. These findings reveal no evidence for prominent polaronic effects, which is at variance with the common beliefs of polaron formation in molecular solids.Comment: 4 pages, 4 figure

Electronic Correlations in Oligo-acene and -thiophene Organic Molecular Crystals

From first principles calculations we determine the Coulomb interaction between two holes on oligo-acene and -thiophene molecules in a crystal, as a function of the oligomer length. The relaxation of the molecular geometry in the presence of holes is found to be small. In contrast, the electronic polarization of the molecules that surround the charged oligomer, reduces the bare Coulomb repulsion between the holes by approximately a factor of two. In all cases the effective hole-hole repulsion is much larger than the calculated valence bandwidth, which implies that at high doping levels the properties of these organic semiconductors are determined by electron-electron correlations.Comment: 5 pages, 3 figure

Intrinsic charge transport on the surface of organic semiconductors

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, mu, and the growth of mu with cooling. The anisotropy of mu 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.Comment: 10 pages, 4 figure

Quantum coherence and carriers mobility in organic semiconductors

We present a model of charge transport in organic molecular semiconductors based on the effects of lattice fluctuations on the quantum coherence of the electronic state of the charge carrier. Thermal intermolecular phonons and librations tend to localize pure coherent states and to assist the motion of less coherent ones. Decoherence is thus the primary mechanism by which conduction occurs. It is driven by the coupling of the carrier to the molecular lattice through polarization and transfer integral fluctuations as described by the hamiltonian of Gosar and Choi. Localization effects in the quantum coherent regime are modeled via the Anderson hamiltonian with correlated diagonal and non-diagonal disorder leading to the determination of the carrier localization length. This length defines the coherent extension of the ground state and determines, in turn, the diffusion range in the incoherent regime and thus the mobility. The transfer integral disorder of Troisi and Orlandi can also be incorporated. This model, based on the idea of decoherence, allowed us to predict the value and temperature dependence of the carrier mobility in prototypical organic semiconductors that are in qualitative accord with experiments

Effect of Intra-molecular Disorder and Inter-molecular Electronic Interactions on the Electronic Structure of Poly-p-Phenylene Vinylene (PPV)

We investigate the role of intra-molecular conformational disorder and inter-molecular electronic interactions on the electronic structure of disorder clusters of poly-p-phenylene vinylene (PPV) oligomers. Classical molecular dynamics is used to determine probable molecular geometries, and first-principle density functional theory (DFT) calculations are used to determine electronic structure. Intra-molecular and inter-molecular effects are disentangled by contrasting results for densely packed oligomer clusters with those for ensembles of isolated oligomers with the same intra-molecular geometries. We find that electron trap states are induced primarily by intra-molecular configuration disorder, while the hole trap states are generated primarily from inter-molecular electronic interactions.Comment: 4 pages, 4 figures. Compile with pdflate

Bias-Dependent Generation and Quenching of Defects in Pentacene

We describe a defect in pentacene single crystals that is created by bias stress and persists at room temperature for an hour in the dark but only seconds with 420nm illumination. The defect gives rise to a hole trap at Ev + 0.38eV and causes metastable transport effects at room temperature. Creation and decay rates of the hole trap have a 0.67eV activation energy with a small (108 s-1) prefactor, suggesting that atomic motion plays a key role in the generation and quenching process.Comment: 10 pages, 3 figure