Ultrafast carrier dynamics in pentacene, functionalized pentacene, tetracene, and rubrene single crystals

We measure the transient photoconductivity in pentacene, functionalized pentacene, tetracene, and rubrene single crystals using optical pump-terahertz probe techniques. In all of the samples studied, we observe subpicosecond charge photogeneration and a peak photoconductive response that increases as the temperature decreases from 297 down to 20 K, indicative of bandlike transport. Similar decay dynamics are observed at room temperature, but at low temperatures the decay dynamics measured in pentacene, rubrene, and tetracene crystals are much faster than those observed in functionalized pentacene crystals, revealing different charge trapping properties.

Electronic Band Structure of Tetracene-TCNQ and Perylene-TCNQ Compounds

The relationship between the crystal structures, band structures, and electronic properties of acene-TCNQ complexes has been investigated. We focus on the newly synthesized crystals of the charge-transfer salt tetracene-TCNQ and similar to it perylene-TCNQ, potentially interesting for realization of ambipolar transport. The band structures were calculated from first principles using density-functional theory (DFT). Despite the similarity in the crystal structures of the acene-TCNQ complexes studied here, the band structures are very different. Hole and electron transport properties are predicted to be equally good in perylene-TCNQ, in contrast to the tetracene-TCNQ, which has good transport properties for electrons only. The estimated degree of charge transfer for tetracene-TCNQ is 0.13e and for perylene-TCNQ 0.46e.

Electrical transport and noise in polyacene semiconductors

Measurements of electrical transport and excess current noise in semiconducting films of polyacenes revealed a superquadratic increase of the current and a sharp peak of the relative noise at voltage values corresponding to the trap-filling transition region. Recently, we formulated an explanation of these findings in terms of trapping and detrapping processes of the injected carriers by deep defect states. This interpretation was based on a phenomenological model that takes as input the measured I-V characteristic curve. Here we introduce a new percolative approach to transport and noise in these materials. In particular we develop two percolation models, differing in the voltage dependence of the trapping and detrapping rates: precisely, one model neglects and the other accounts for the Poole-Frenkel effect.We then discuss the results of both models in connections with experimental finding

Effect of the intermolecular thermal motions on the tail of the electronic density of states in polyacene crystals

The thermal fluctuation of the intermolecular hopping integral in the series of polyacene crystals (naphthalene, anthracene, tetracene, pentacene) was evaluated computationally using a combined molecular dynamics and quantum chemistry approach. It was shown that these large fluctuations can manifest themselves in a temperature-dependent relatively broad tail of the density of states extending from the valence band into the gap. It was also shown that this tail accounts for a large fraction of all states in the valence band and therefore it may be essential for accurately describing the charge transport and optical properties