Electronic properties and structure of single crystal perylene.

The transport properties of electronic devices made from single crystalline molecular semiconductors typically outperform those composed of thin-films of the same material. To further understand the superiority of these extrinsic device properties, an understanding of the intrinsic electronic structure and properties of the organic semiconductor is necessary. An investigation of the electronic structure and properties of single crystal α-phase perylene (C20H12), a five-ringed aromatic molecule, is presented using angle-resolved ultraviolet photoemission, x-ray photoelectron spectroscopy (XPS), and field-effect transistor measurements. Key aspects of the electronic structure of single crystal α-perylene critical to charge transport are determined, including the energetic location of the highest occupied molecular orbital (HOMO), the HOMO bandwidth, and surface work function. In addition, using high resolution XPS, we can distinguish between inequivalent carbon atoms within the perylene crystal and, from the shake-up satellite structure in XPS, gain insight into the intramolecular properties in α-perylene. From the device measurements, the charge carrier mobility of α-perylene is found to depend on the device structure and the choice of dielectric, with values in the range of 10-3 cm2 V-1 s-1.

Vibrational properties of organic donor-acceptor molecular crystals: Anthracene-pyromellitic-dianhydride (PMDA) as a case study.

We establish a reliable quantum-mechanical approach to evaluate the vibrational properties of donor-acceptor molecular crystals. The anthracene-PMDA (PMDA = pyromellitic dianhydride) crystal, where anthracene acts as the electron donor and PMDA as the electron acceptor, is taken as a representative system for which experimental non-resonance Raman spectra are also reported. We first investigate the impact that the amount of nonlocal Hartree-Fock exchange (HFE) included in a hybrid density functional has on the geometry, normal vibrational modes, electronic coupling, and electron-vibrational (phonon) couplings. The comparison between experimental and theoretical Raman spectra indicates that the results based on the αPBE functional with 25%-35% HFE are in better agreement with the experimental results compared to those obtained with the pure PBE functional. Then, taking αPBE with 25% HFE, we assign the vibrational modes and examine their contributions to the relaxation energy related to the nonlocal electron-vibration interactions. The results show that the largest contribution (about 90%) is due to electron interactions with low-frequency vibrational modes. The relaxation energy in anthracene-PMDA is found to be about five times smaller than the electronic coupling.

Freezing-in orientational disorder induces crossover from thermally-activated to temperature-independent transport in organic semiconductors.

The crystalline structure of organic materials dictates their physical properties, but while significant research effort is geared towards understanding structure-property relationships in such materials, the details remain unclear. Many organic crystals exhibit transitions in their electrical properties as a function of temperature. One example is the 1:1 charge-transfer complex trans--stilbene-2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane. Here we show that the mobility and resistivity of this material undergo a transition from being thermally activated at temperatures above 235 K to being temperature independent at low temperatures. On the basis of our experimental and theoretical results, we attribute this behaviour to the presence of a glass-like transition and the accompanied freezing-in of orientational disorder of the stilbene molecule.

On the mechanism of charge transport in pentacene.

Terahertz transient conductivity measurements are performed on pentacene single crystals, which directly demonstrate a strong coupling of charge carriers to low frequency molecular motions with energies centered around 1.1 THz. We present evidence that the strong coupling to low frequency motions is the factor limiting the conductivity in these organic semiconductors. Our observations explain the apparent paradox of the "bandlike" temperature dependence of the conductivity beyond the validity limit of the band model.

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.

Contact-induced crystallinity for high-performance soluble acene-based transistors and circuits.

The use of organic materials presents a tremendous opportunity to significantly impact the functionality and pervasiveness of large-area electronics. Commercialization of this technology requires reduction in manufacturing costs by exploiting inexpensive low-temperature deposition and patterning techniques, which typically lead to lower device performance. We report a low-cost approach to control the microstructure of solution-cast acene-based organic thin films through modification of interfacial chemistry. Chemically and selectively tailoring the source/drain contact interface is a novel route to initiating the crystallization of soluble organic semiconductors, leading to the growth on opposing contacts of crystalline films that extend into the transistor channel. This selective crystallization enables us to fabricate high-performance organic thin-film transistors and circuits, and to deterministically study the influence of the microstructure on the device characteristics. By connecting device fabrication to molecular design, we demonstrate that rapid film processing under ambient room conditions and high performance are not mutually exclusive.

The effect of oxygen exposure on pentacene electronic structure.

We use ultraviolet photoelectron spectroscopy to investigate the effect of oxygen and air exposure on the electronic structure of pentacene single crystals and thin films. It is found that O(2) and water do not react noticeably with pentacene, whereas singlet oxygen/ozone readily oxidize the organic compound. Also, we obtain no evidence for considerable p-type doping of pentacene by O(2) at low pressure. However, oxygen exposure lowers the hole injection barrier at the interface between Au and pentacene by 0.25 eV, presumably due to a modification of the Au surface properties.