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A rapidly growing interest in organic bioelectronic applications has spurred the development of a wide variety of organic mixed ionic‐electronic conductors. While these new mixed conductors have enabled the community to interface organic electronics with biological systems and efficiently transduce biological signals (ions) into electronic signals, the current materials selection does not offer sufficient selectivity towards specific ions of biological relevance without the use of auxiliary components such as ion‐selective membranes. Here, we present the molecular design of an n‐type (electron‐transporting) perylene diimide semiconductor material decorated with pendant oligoether groups to facilitate interactions with cations such as Na+ and K+. Using the cyclic 15‐crown‐5 oligoether motif, we find that the resulting mixed conductor PDI‐crown displays a strong dependence on the size of the electrolyte cation when tested in an organic electrochemical transistor configuration. In stark contrast to the low current response on the order of 1 μA observed with aqueous sodium chloride, a nearly 200‐fold increase in current is observed with aqueous potassium chloride. We ascribe the high selectivity to extended molecular aggregation and therefore efficient charge transport in the presence of K+ due to a favourable sandwich‐like structure between two adjacent 15‐crown‐5 motifs and the potassium ion. [ABSTRACT FROM AUTHOR]

Solid‐state molecular arrangement has been recognized as the most important role in the charge transport properties of organic semiconductors. Although highly ordered molecular stacking is achieved in single crystals, maintaining single‐crystal molecular packing in solution‐processed thin films remains a significant challenge. Herein, a new type of n‐type organic semiconductors based on an asymmetric fluoranthene imide unit is reported, whose intermolecular packing and aggregation behavior in the thin film state can be effectively controlled by regulating the cyano substitution sites and alkyl chain types in the imide group. F10 with cyano groups at 4,9‐sites and branched 2‐ethylhexyl chain encouragingly shows a highly ordered single‐crystal‐like molecular packing in solution‐processed thin film after thermal annealing, and thus the resulting organic field‐effect transistors exhibit impressive charge transport performance, with the electron mobility as high as 0.116 cm2 V−1 s−1. This work opens a new avenue for developing high‐performance solution‐processed n‐type semiconductors. [ABSTRACT FROM AUTHOR]

Developing novel n‐type organic semiconductors is an on‐going research endeavour, given their pivotal roles in organic electronics and their relative scarcity compared to p‐type counterparts. In this study, a new strategy was employed to synthesize n‐type organic semiconductors featuring a fully fused conjugated backbone. By attaching two sets of adjacent amino and formyl groups to the indacenodithiophene‐based central cores and triggering a tandem reaction sequence of a Knoevenagel condensation‐intramolecular cyclization, DFA1 and DFA2 were realized. The solution‐processed organic field effect transistors based on DFA1 exhibited unipolar n‐type transport character with a decent electron mobility of ca. 0.10 cm2 V−1 s−1 (ca. 0.038 cm2 V−1 s−1 for DFA2 based devices). When employing DFA1 as a third component in organic solar cells, a high power conversion efficiency of 19.2 % can be achieved in ternary devices fabricated with PM6 : L8‐BO : DFA1. This work provides a new pathway in the molecular engineering of n‐type organic semiconductors, propelling relevant research forward. [ABSTRACT FROM AUTHOR]

Perylenetetracarboxylic diimide (PTCDI) is an n-type organic semiconductor molecule that has been widely utilized in numerous applications such as photocatalysis and field-effect transistors. Polarizability and dipole moment, which are inherent properties of molecules, are important parameters that determine their responses to external electric and optical fields, physical properties, and reactivity. These parameters are fundamentally important for the design of innovative materials. In this study, the effects of external electric fields on absorption and fluorescence spectra were investigated to obtain the PTCDI parameters. The PTCDI substituted by an octyl group (N,N′-Dioctyl-3,4,9,10-perylenedicarboximide) dispersed in a polymethyl methacrylate (PMMA) matrix was studied in this work. The features of vibronic progression in the absorption spectrum were analogous to those observed in solution. The red shift of the absorption band caused by the Stark effect was mainly observed in the presence of an external electric field. Changes in parameters such as the dipole moment and polarizability between the ground and the Franck–Condon excited states of the PTCDI monomer were determined. The fluorescence spectrum shows a contribution from a broad fluorescence band at wavelengths longer than the monomer fluorescence band. This broad fluorescence is ascribed to the excimer-like fluorescence of PTCDI. The effects of the electric field on the fluorescence spectrum, known as the Stark fluorescence or electrofluorescence spectrum, were measured. Fluorescence quenching is observed in the presence of an external electric field. The change in the polarizability of the monomer fluorescence band is in good agreement with that of the electroabsorption spectrum. A larger change in the polarizability was observed for the excimer-like fluorescence band than that for the monomer band. This result is consistent with exciton delocalization between PTCDI molecules in the excimer-like state. [ABSTRACT FROM AUTHOR]

The organic electrochemical transistor (OECT) is one of the most versatile building blocks within the bioelectronics device toolbox. While p‐type organic semiconductors have progressed as OECT channel materials, only a few n‐type semiconductors have been reported, precluding the development of advanced sensor‐integrated OECT‐based complementary circuits. Herein, green aldol polymerization is uses to synthesize lactone‐based n‐type conjugated polymers. Fluorination of the lactone‐based acceptor endows a fully locked backbone with a low‐lying lowest unoccupied molecular orbital, facilitating efficient ionic‐to‐electronic charge coupling. The resulting polymer has a record‐high n‐type OECT performance with a high product of mobility and capacitance (µC* = 108 F cm−1 V−1 s−1), excellent mobility (0.912 cm2 V−1 s−1), low threshold voltage (0.02 V), and fast switching speed (τON, τOFF = 336 µs,108 µs). This work demonstrates two types of device architectures and applications enabled by the high performance of this n‐type OECT, i.e., an artificial synapse and a complementary amplifier for detecting α‐synuclein, a potential biomarker of Parkinson's disease. This study shows that materials that enable high gain and fast speed n‐type OECTs can be developed via a green polymerization route, and the diverse form factors that these devices take promise for exploration of other application areas. [ABSTRACT FROM AUTHOR]

Perylenetetracarboxylic diimide (PTCDI) is an n-type organic semiconductor molecule that has been widely utilized in numerous applications such as photocatalysis and field-effect transistors. Polarizability and dipole moment, which are inherent properties of molecules, are important parameters that determine their responses to external electric and optical fields, physical properties, and reactivity. These parameters are fundamentally important for the design of innovative materials. In this study, the effects of external electric fields on absorption and fluorescence spectra were investigated to obtain the PTCDI parameters. The PTCDI substituted by an octyl group (N,N′-Dioctyl-3,4,9,10-perylenedicarboximide) dispersed in a polymethyl methacrylate (PMMA) matrix was studied in this work. The features of vibronic progression in the absorption spectrum were analogous to those observed in solution. The red shift of the absorption band caused by the Stark effect was mainly observed in the presence of an external electric field. Changes in parameters such as the dipole moment and polarizability between the ground and the Franck–Condon excited states of the PTCDI monomer were determined. The fluorescence spectrum shows a contribution from a broad fluorescence band at wavelengths longer than the monomer fluorescence band. This broad fluorescence is ascribed to the excimer-like fluorescence of PTCDI. The effects of the electric field on the fluorescence spectrum, known as the Stark fluorescence or electrofluorescence spectrum, were measured. Fluorescence quenching is observed in the presence of an external electric field. The change in the polarizability of the monomer fluorescence band is in good agreement with that of the electroabsorption spectrum. A larger change in the polarizability was observed for the excimer-like fluorescence band than that for the monomer band. This result is consistent with exciton delocalization between PTCDI molecules in the excimer-like state.