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Register a new userFreeing electrons from extrinsic and intrinsic disorder yields band-like transport in n-type organic semiconductors
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Charge transport in organic semiconductors is notoriously extremely sensitive to the presence of disorder, both intrinsic and extrinsic, especially for n-type materials. Intrinsic dynamic disorder stems from large thermal fluctuations both in intermolecular transfer integrals and (molecular) site energies in weakly interacting van der Waals solids and sources transient localization of the charge carriers. The molecular vibrations that drive transient localization typically operate at low-frequency (< a-few-hundred cm-1), which renders it difficult to assess them experimentally. Hitherto, this has prevented the identification of clear molecular design rules to control and reduce dynamic disorder. In addition, the disorder can also be extrinsic, being controlled by the gate insulator dielectric properties. Here we report on a comprehensive study of charge transport in two closely related n-type molecular organic semiconductors using a combination of temperature-dependent inelastic neutron scattering and photoelectron spectroscopy corroborated by electrical measurements, theory and simulations. We provide unambiguous evidence that ad hoc molecular design enables to free the electron charge carriers from both intrinsic and extrinsic disorder to ultimately reach band-like electron transport.
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Charge transport in organic semiconductors is notoriously extremely sensitive to the presence of disorder, both internal and external (i.e. related to the interactions with the dielectric layer), especially for n-type materials. Internal dynamic disorder stems from large thermal fluctuations both in intermolecular transfer integrals and (molecular) site energies in weakly interacting van der Waals solids and sources transient localization of the charge carriers. The molecular vibrations that drive transient localization typically operate at low-frequency (< a-few-hundred cm-1), which renders it difficult to assess them experimentally. Hitherto, this has prevented the identification of clear molecular design rules to control and reduce dynamic disorder. In addition, the disorder can also be external, being controlled by the gate insulator dielectric properties. Here we report on a comprehensive study of charge transport in two closely related n-type molecular organic semiconductors using a combination of temperature-dependent inelastic neutron scattering and photoelectron spectroscopy corroborated by electrical measurements, theory and simulations. We provide unambiguous evidence that ad hoc molecular design enables to free the electron charge carriers from both internal and external disorder to ultimately reach band-like electron transport.
We explore the charge transport mechanism in organic semiconductors based on a model that accounts for the thermal intermolecular disorder at work in pure crystalline compounds, as well as extrinsic sources of disorder that are present in current experimental devices. Starting from the Kubo formula, we develop a theoretical framework that relates the time-dependent quantum dynamics of electrons to the frequency-dependent conductivity. The electron mobility is then calculated through a relaxation time approximation that accounts for quantum localization corrections beyond Boltzmann theory, and allows us to efficiently address the interplay between highly conducting states in the band range and localized states induced by disorder in the band tails. The emergence of a transient localization phenomenon is shown to be a general feature of organic semiconductors, that is compatible with the bandlike temperature dependence of the mobility observed in pure compounds. Carrier trapping by extrinsic disorder causes a crossover to a thermally activated behavior at low temperature, which is progressively suppressed upon increasing the carrier concentration, as is commonly observed in organic field-effect transistors. Our results establish a direct connection between the localization of the electronic states and their conductive properties, formalizing phenomenological considerations that are commonly used in the literature.
We probe charge photogeneration and subsequent recombination dynamics in neat regioregular poly(3-hexylthiophene) films over six decades in time by means of time-resolved photoluminescence spectroscopy. Exciton dissociation at 10K occurs extrinsically at interfaces between molecularly ordered and disordered domains. Polaron pairs thus produced recombine by tunnelling with distributed rates governed by the distribution of electron-hole radii. Quantum-chemical calculations suggest that hot-exciton dissociation at such interfaces results from a high charge-transfer character.
Single-crystal organic field-effect transistors (OFETs) based on p-channel molecular semiconductors have led to breakthrough carrier mobilities and to the observation of band-like transport. These results represent the limit in our quest for the ultimate OFET performance. However, band-like transport has not been reported for n-channel OFETs and, for p-channel transistors, it is not understood why it occurs only for certain molecular materials. Here we report band-like electron transport for n-channel OFETs based on PDIF-CN2 single-crystals. Devices with different gate dielectrics - vacuum, Cytop, PMMA - are compared and we find that the performance is suppressed for those with larger dielectric constant. This phenomenon parallels that observed for holes in p-channel OFETs, however, the magnitude of the suppression is smaller, an effect that can be rationalized by the semiconductor molecular structure and crystal packing. A quantitative analysis of our findings, together with results on different high-quality p-channel transistors, indicates the importance of the interplay between the semiconductor molecular polarizability and the structure of the charge transport layers in the crystal, as a key factor enabling band-like transport. Based on these considerations, we suggest unprecedented structure-property relationships useful for performance optimization of high-mobility organic transistors.
Fully understanding the properties of n-type ferromagnetic semiconductors (FMSs), complementary to the mainstream p-type ones, is a challenging goal in semiconductor spintronics because ferromagnetism in n-type FMSs is theoretically non-trivial. Soft-x-ray angle-resolved photoemission spectroscopy (SX-ARPES) is a powerful approach to examine the mechanism of carrier-induced ferromagnetism in FMSs. Here our SX-ARPES study on the prototypical n-type FMS (In,Fe)As reveals the entire band structure including the Fe-3d impurity bands (IBs) and the host InAs ones, and provides direct evidence for electron occupation of the InAs-derived conduction band (CB). A minority-spin Fe-3d IB is found to be located just below the conduction-band minimum (CBM). The IB is formed by the hybridization of the unoccupied Fe-3d states with the occupied CBM of InAs in a spin-dependent way, resulting in the large spin polarization of CB. The band structure with the IB is varied with band filling, which cannot be explained by the rigid-band picture, suggesting a unified picture for realization of carrier-induced ferromagnetism in FMS materials.
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