The charge mobility of molecular semiconductors is limited by the large fluctuation of intermolecular transfer integrals, often referred to as off-diagonal dynamic disorder, which causes transient ...localization of the carriers' eigenstates. Using a recently developed theoretical framework, we show here that the electronic structure of the molecular crystals determines its sensitivity to intermolecular fluctuations. We build a map of the transient localization lengths of high-mobility molecular semiconductors to identify what patterns of nearest-neighbour transfer integrals in the two-dimensional (2D) high-mobility plane protect the semiconductor from the effect of dynamic disorder and yield larger mobility. Such a map helps rationalizing the transport properties of the whole family of molecular semiconductors and is also used to demonstrate why common textbook approaches fail in describing this important class of materials. These results can be used to rapidly screen many compounds and design new ones with optimal transport characteristics.
A relation derived from the Kubo formula shows that optical conductivity measurements below the gap frequency in doped semiconductors can be used to probe directly the time-dependent quantum dynamics ...of charge carriers. This allows to extract fundamental quantities such as the elastic and inelastic scattering rates, as well as the localization length in disordered systems. When applied to crystalline organic semiconductors, an incipient electron localization caused by large dynamical lattice disorder is unveiled, implying a breakdown of semiclassical transport.
The consequences of several microscopic interactions on the photoemission spectra of crystalline organic semiconductors are studied theoretically. It is argued that their relative roles can be ...disentangled by analyzing both their temperature and their momentum-energy dependence. Our analysis shows that the polaronic thermal band narrowing, which is the foundation of most theories of electrical transport in organic semiconductors, is inconsistent in the range of microscopic parameters appropriate for these materials. An alternative scenario is proposed to explain the experimental trends.
Bloch-Boltzmann transport theory fails to describe the carrier diffusion in current crystalline organic semiconductors, where the presence of large-amplitude thermal molecular motions causes ...substantial dynamical disorder. The charge transport mechanism in this original situation is now understood in terms of a transient localization of the carriers' wave functions, whose applicability is, however, limited to the strong disorder regime. To deal with the ever-improving performances of new materials, we develop here a unified theoretical framework that includes transient localization theory as a limiting case and smoothly connects with the standard band description when molecular disorder is weak. The theory, which specifically addresses the emergence of dynamical localization corrections to semiclassical transport, is used to determine a "transport phase diagram" of high-mobility organic semiconductors.
The localization of charge carriers by electronic repulsion was suggested by Mott in the 1930s to explain the insulating state observed in supposedly metallic NiO. The Mott metal-insulator transition ...has been subject of intense investigations ever since
-not least for its relation to high-temperature superconductivity
. A detailed comparison to real materials, however, is lacking because the pristine Mott state is commonly obscured by antiferromagnetism and a complicated band structure. Here we study organic quantum spin liquids, prototype realizations of the single-band Hubbard model in the absence of magnetic order. Mapping the Hubbard bands by optical spectroscopy provides an absolute measure of the interaction strength and bandwidth-the crucial parameters that enter calculations. In this way, we advance beyond conventional temperature-pressure plots and quantitatively compose a generic phase diagram for all genuine Mott insulators based on the absolute strength of the electronic correlations. We also identify metallic quantum fluctuations as a precursor of the Mott insulator-metal transition, previously predicted but never observed. Our results suggest that all relevant phenomena in the phase diagram scale with the Coulomb repulsion U, which provides a direct link to unconventional superconductivity in cuprates and other strongly correlated materials.
The electrodynamic response of organic spin liquids with highly frustrated triangular lattices has been measured in a wide energy range. While the overall optical spectra of these Mott insulators are ...governed by transitions between the Hubbard bands, distinct in-gap excitations can be identified at low temperatures and frequencies, which we attribute to the quantum-spin-liquid state. For the strongly correlated β^{'}-EtMe_{3}SbPd(dmit)_{2}_{2}, we discover enhanced conductivity below 175 cm^{-1}, comparable to the energy of the magnetic coupling J≈250 K. For ω→0, these low-frequency excitations vanish faster than the charge-carrier response subject to Mott-Hubbard correlations, resulting in a dome-shaped band peaked at 100 cm^{-1}. Possible relations to spinons, magnons, and disorder are discussed.
Background Studies on marine community dynamics and population structures are limited by the lack of exhaustive knowledge on the larval dispersal component of connectivity. Genetic data represents a ...powerful tool in understanding such processes in the marine realm. When dealing with dispersion and connectivity in marine ecosystems, many evidences show patterns of genetic structure that cannot be explained by any clear geographic trend and may show temporal instability. This scenario is usually referred to as chaotic genetic patchiness, whose driving mechanisms are recognized to be selection, temporal shifts in local population dynamics, sweepstakes reproductive success and collective dispersal. In this study we focused on the marbled crab Pachygrapsus marmoratus that inhabits the rocky shores of the Mediterranean Sea, Black Sea and East Atlantic Ocean, and disperses through planktonic larvae for about 1 month. P. marmoratus exhibits unexpectedly low connectivity levels at local scale, although well-defined phylogeographic patterns across the species’ distribution range were described. This has been explained as an effect of subtle geographic barriers or due to sweepstake reproductive success. In order to verify a chaotic genetic patchiness scenario, and to explore mechanisms underlying it, we planned our investigation within the Ligurian Sea, an isolated basin of the western Mediterranean Sea, and we genotyped 321 individuals at 11 microsatellite loci. Results We recorded genetic heterogeneity among our Ligurian Sea samples with the occurrence of genetic clusters not matching the original populations and a slight inter-population divergence, with the geographically most distant populations being the genetically most similar ones. Moreover, individuals from each site were assigned to all the genetic clusters. We also recorded evidences of self-recruitment and a higher than expected within-site kinship. Conclusions Overall, our results suggest that the chaotic genetic patchiness we found in P. marmoratus Ligurian Sea populations is the result of a combination of differences in reproductive success, en masse larval dispersion and local larval retention. This study defines P. marmoratus as an example of marine spawner whose genetic pool is not homogenous at population level, but rather split in a chaotic mosaic of slightly differentiated genetic patches derived from complex and dynamic ecological processes.
In organic field-effect transistors (FETs), charges move near the surface of an organic semiconductor, at the interface with a dielectric. In the past, the nature of the microscopic motion of charge ...carriers--which determines the device performance--has been related to the quality of the organic semiconductor. Recently, it was discovered that the nearby dielectric also has an unexpectedly strong influence. The mechanisms responsible for this influence are not understood. To investigate these mechanisms, we have studied transport through organic single-crystal FETs with different gate insulators. We find that the temperature dependence of the mobility evolves from metallic-like to insulating-like with increasing dielectric constant of the insulator. The phenomenon is accounted for by a two-dimensional Fröhlich polaron model that quantitatively describes our observations and shows that increasing the dielectric polarizability results in a crossover from the weak to the strong polaronic coupling regime. This represents a considerable step forward in our understanding of transport through organic transistors, and identifies a microscopic physical process with a large influence on device performance.
By comparing photoemission spectroscopy with a nonperturbative dynamical mean field theory extension to many-body ab initio calculations, we show in the prominent case of pentacene crystals that an ...excellent agreement with experiment for the bandwidth, dispersion, and lifetime of the hole carrier bands can be achieved in organic semiconductors, provided that one properly accounts for the coupling to molecular vibrational modes and the presence of disorder. Our findings rationalize the growing experimental evidence that even the best band structure theories based on a many-body treatment of electronic interactions cannot reproduce the experimental photoemission data in this important class of materials.
Despite the great interest organic spintronics has recently attracted, there is only a partial understanding of the fundamental physics behind electron spin relaxation in organic semiconductors. ...Mechanisms based on hyperfine interaction have been demonstrated, but the role of the spin-orbit interaction remains elusive. Here, we report muon spin spectroscopy and time-resolved photoluminescence measurements on two series of molecular semiconductors in which the strength of the spin-orbit interaction has been systematically modified with a targeted chemical substitution of different atoms at a particular molecular site. We find that the spin-orbit interaction is a significant source of electron spin relaxation in these materials.
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