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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.
Two-dimensional atomic crystals are extensively studied in recent years due to their exciting physics and device applications. However, a molecular counterpart, with scalable processability and competitive device performance, is still challenging. He
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 diso
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 intermo
We use photoemission spectroscopy to study electronic structures of pristine and K-doped solid picene. The valence band spectrum of pristine picene consists of three main features with no state at the Fermi level (EF), while that of K-doped picene ha
The electronic and optical properties of the paradigmatic F4TCNQ-doped pentacene in the low-doping limit are investigated by a combination of state-of-the-art many-body emph{ab initio} methods accounting for environmental screening effects, and a car