Enantiopure Dinaphtho[2,3-b:2,3-f]thieno[3,2-b]thiophenes: Reaching High Magnetoresistance Effect in OFETs.

Chiral molecules are known to behave as spin filters due to the chiral induced spin selectivity (CISS) effect. Chirality can be implemented in molecular semiconductors in order to study the role of the CISS effect in charge transport and to find new materials for spintronic applications. In this study, the design and synthesis of a new class of enantiopure chiral organic semiconductors based on the well-known dinaphtho[2,3-b:2,3-f]thieno[3,2-b]thiophene (DNTT) core functionalized with chiral alkyl side chains is presented. When introduced in an organic field-effect transistor (OFET) with magnetic contacts, the two enantiomers, (R)-DNTT and (S)-DNTT, show an opposite behavior with respect to the relative direction of the magnetization of the contacts, oriented by an external magnetic field. Each enantiomer displays an unexpectedly high magnetoresistance over one preferred orientation of the spin current injected from the magnetic contacts. The result is the first reported OFET in which the current can be switched on and off upon inversion of the direction of the applied external magnetic field. This work contributes to the general understanding of the CISS effect and opens new avenues for the introduction of organic materials in spintronic devices.

A robust vertical nanoscaffold for recyclable, paintable, and flexible light-emitting devices.

Organic light-emitting devices are key components for emerging opto- and nanoelectronics applications including health monitoring and smart displays. Here, we report a foldable inverted polymer light-emitting diode (iPLED) based on a self-suspended asymmetrical vertical nanoscaffold replacing the conventional sandwich-like structured LEDs. Our empty vertical-yet-open nanoscaffold exhibits excellent mechanical robustness, proven by unaltered leakage current when applying 1000 cycles of 40-kilopascal pressure loading/unloading, sonication, and folding, with the corresponding iPLEDs displaying a brightness as high as 2300 candela per square meter. By using photolithography and brush painting, arbitrary emitting patterns can be generated via a noninvasive and mask-free process with individual pixel resolution of 10 µm. Our vertical nanoscaffold iPLED can be supported on flexible polyimide foils and be recycled multiple times by washing and refilling with a different conjugated polymer capable of emitting light of different color. This technology combines the traits required for the next generation of high-resolution flexible displays and multifunctional optoelectronics.

Dinaphthotetrathienoacenes: Synthesis, Characterization, and Applications in Organic Field-Effect Transistors.

The charge transport of crystalline organic semiconductors is limited by dynamic disorder that tends to localize charges. It is the main hurdle to overcome in order to significantly increase charge carrier mobility. An innovative design that combines a chemical structure based on sulfur-rich thienoacene with a solid-state herringbone (HB) packing is proposed and the synthesis, physicochemical characterization, and charge transport properties of two new thienoacenes bearing a central tetrathienyl core fused with two external naphthyl rings: naphtho[2,3-b]thieno-[2''',3''':4'',5'']thieno[2″,3″:4',5']thieno[3',2'-b]naphtho[2,3-b]thiophene (DN4T) and naphtho[1,2-b]thieno-[2''',3''':4'',5'']thieno[2'',3'':4',5']thieno[3',2'-b]naphtho[1,2-b]thiophene are presented. Both compounds crystallize with a HB pattern structure and present transfer integrals ranging from 33 to 99 meV (for the former) within the HB plane of charge transport. Molecular dynamics simulations point toward an efficient resilience of the transfer integrals to the intermolecular sliding motion commonly responsible for strong variations of the electronic coupling in the crystal. Best device performances are reached with DN4T with hole mobility up to µ = 2.1 cm2 V-1 s-1 in polycrystalline organic field effect transistors, showing the effectiveness of the electronic coupling enabled by the new aromatic core. These promising results pave the way to the design of high-performing materials based on this new thienoacene, notably through the introduction of alkyl side-chains.

High-Performance Humidity Sensing in π-Conjugated Molecular Assemblies through the Engineering of Electron/Proton Transport and Device Interfaces.

The development of systems capable of responding to environmental changes, such as humidity, requires the design and assembly of highly sensitive and efficiently transducing elements. Such a challenge can be mastered only by disentangling the role played by each component of the responsive system, thus ultimately achieving high performance by optimizing the synergistic contribution of all functional elements. Here, we designed and synthesized a novel [1]benzothieno[3,2-b][1]benzothiophene derivative equipped with hydrophilic oligoethylene glycol lateral chains (OEG-BTBT) that can electrically transduce subtle changes in ambient humidity with high current ratios (>104) at low voltages (2 V), reaching state-of-the-art performance. Multiscale structural, spectroscopical, and electrical characterizations were employed to elucidate the role of each device constituent, viz., the active material's BTBT core and OEG side chains, and the device interfaces. While the BTBT molecular core promotes the self-assembly of (semi)conducting crystalline films, its OEG side chains are prone to adsorb ambient moisture. These chains act as hotspots for hydrogen bonding with atmospheric water molecules that locally dissociate when a bias voltage is applied, resulting in a mixed electronic/protonic long-range conduction throughout the film. Due to the OEG-BTBT molecules' orientation with respect to the surface and structural defects within the film, water molecules can access the humidity-sensitive sites of the SiO2 substrate surface, whose hydrophilicity can be tuned for an improved device response. The synergistic chemical engineering of materials and interfaces is thus key for designing highly sensitive humidity-responsive electrical devices whose mechanism relies on the interplay of electron and proton transport.

Boosting the electronic and catalytic properties of 2D semiconductors with supramolecular 2D hydrogen-bonded superlattices.

The electronic properties of two-dimensional semiconductors can be strongly modulated by interfacing them with atomically precise self-assembled molecular lattices, yielding hybrid van der Waals heterostructures (vdWHs). While proof-of-concepts exploited molecular assemblies held together by lateral unspecific van der Waals interactions, the use of 2D supramolecular networks relying on specific non-covalent forces is still unexplored. Herein, prototypical hydrogen-bonded 2D networks of cyanuric acid (CA) and melamine (M) are self-assembled onto MoS2 and WSe2 forming hybrid organic/inorganic vdWHs. The charge carrier density of monolayer MoS2 exhibits an exponential increase with the decreasing area occupied by the CA·M unit cell, in a cooperatively amplified process, reaching 2.7 × 1013 cm-2 and thereby demonstrating strong n-doping. When the 2D CA·M network is used as buffer layer, a stark enhancement in the catalytic activity of monolayer MoS2 for hydrogen evolution reactions is observed, outperforming the platinum (Pt) catalyst via gate modulation.

2D MXene-Molecular Hybrid Additive for High-Performance Ambipolar Polymer Field-Effect Transistors and Logic Gates.

MXenes are highly conductive layered materials that are attracting a great interest for high-performance opto-electronics, photonics, and energy applications.. Their non-covalent functionalization with ad hoc molecules enables the production of stable inks of 2D flakes to be processed in thin-films. Here, the formation of stable dispersions via the intercalation of Ti3 C2 Tx with didecyldimethyl ammonium bromide (DDAB) yielding Ti3 C2 Tx -DDAB, is demonstrated. Such functionalization modulates the properties of Ti3 C2 Tx , as evidenced by a 0.47 eV decrease of the work function. It is also shown that DDAB is a powerful n-dopant capable of enhancing electron mobility in conjugated polymers and 2D materials. When Ti3 C2 Tx -DDAB is blended with poly(diketopyrrolopyrrole-co-selenophene) [(PDPP-Se)], a simultaneous increase by 170% and 152% of the hole and electron field-effect mobilities, respectively, is observed, compared to the neat conjugated polymer, with values reaching 2.0 cm2 V-1 s-1 . By exploiting the balanced ambipolar transport of the Ti3 C2 Tx -DDAB/PDPP-Se hybrid, complementary metal-oxide-semiconductor (CMOS) logic gates are fabricated that display well-centered trip points and good noise margin (64.6% for inverter). The results demonstrate that intercalant engineering represents an efficient strategy to tune the electronic properties of Ti3 C2 Tx yielding functionalized MXenes for polymer transistors with unprecedented performances and functions.