The charge transport in molecular systems is governed by a series of carrier-molecule quantum interactions, which result in a broad set of chemical and physical phenomena. The precise control of such phenomena is one of the main challenges toward the development of novel device concepts. In molecular systems, direct tunneling across 1−10 nm barriers and activated hopping over longer distances have been described as the main charge transport mechanisms. The continuous transition from one mechanism to the other, by increasing the transport distance, has mainly been reported for molecular chains covalently bonded to the electrodes. In elementary molecular junctions, like those formed by physisorbed organic semiconductor thin films, such transition remains unclear. Here, we report the first experimental evidence for sequential, long-range coherent tunneling across physisorbed ensembles by investigating the charge transport in copper phthalocyanine layers (5−60 nm thick films). Like observed for chemisorbed molecules, our junction exhibits a gradual transition from coherent tunneling to activated transport in the 10−22 nm thickness range. The present work contributes to connect the quantum transport to diffusive-related phenomena in such an elementary organic system.

The effective utilization of vertical organic transistors in high current density applications demands further reduction of channel length (given by the thickness of the organic semiconducting layer and typically reported in the 100 nm range) along with the optimization of the source electrode structure. Here we present a viable solution by applying rolled-up metallic nanomembranes as the drain-electrode (which enables the incorporation of few nanometer-thick semiconductor layers) and by lithographically patterning the source-electrode. Our vertical organic transistors operate at ultra-low voltages and demonstrate high current densities (~0.5 A cm−2) that are found to depend directly on the number of source edges, provided the source perforation gap is wider than 250 nm. We anticipate that further optimization of device structure can yield higher current densities (~10 A cm−2). The use of rolled-up drain-electrode also enables sensing of humidity and light which highlights the potential of these devices to advance next-generation sensing technologies.

Memristors (MRs) are considered promising devices with the enormous potential to replace complementary metal-oxide-semiconductor (CMOS) technology, which approaches the scale limit. Efforts to fabricate MRs-based hybrid materials may result in suitable operating parameters coupled to high mechanical flexibility and low cost. Metal–organic frameworks (MOFs) arise as a favorable candidate to cover such demands. The step-by-step growth of MOFs structures on functionalized surfaces, called surface-supported metal–organic frameworks (SURMOFs), opens the possibility for designing new applications in strategic fields such as electronics, optoelectronics, and energy harvesting. However, considering the MRs architecture, the typical high porosity of these hybrid materials may lead to short-circuited devices easily. In this sense, here, it is reported for the first time the integration of SURMOF films in rolled-up scalable-functional devices. A freestanding metallic nanomembrane provides a robust and self-adjusted top mechanical contact on the SURMOF layer. The electrical characterization reveals an ambipolar resistive switching mediated by the humidity level with low-power consumption. The electronic properties are investigated with density functional theory (DFT) calculations. Furthermore, the device concept is versatile, compatible with the current parallelism demands of integration, and transcends the challenge in contacting SURMOF films for scalable-functional devices.

Organic electrochemical transistors (OECTs) are technologically relevant devices presenting high susceptibility to physical stimulus, chemical functionalization, and shape changes—jointly to versatility and low production costs. The OECT capability of liquid‐gating addresses both electrochemical sensing and signal amplification within a single integrated device unit. However, given the organic semiconductor time‐consuming doping process and their usual low field‐effect mobility, OECTs are frequently considered low‐end category devices. Toward high‐performance OECTs, microtubular electrochemical devices based on strain‐engineering are presented here by taking advantage of the exclusive shape features of self‐curled nanomembranes. Such novel OECTs outperform the state‐of‐the‐art organic liquid‐gated transistors, reaching lower operating voltage, improved ion doping, and a signal amplification with a >104 intrinsic gain. The multipurpose OECT concept is validated with different electrolytes and distinct nanometer‐thick molecular films, namely, phthalocyanine and thiophene derivatives. The OECTs are also applied as transducers to detect a biomarker related to neurological diseases, the neurotransmitter dopamine. The self‐curled OECTs update the premises of electrochemical energy conversion in liquid‐gated transistors, yielding a substantial performance improvement and new chemical sensing capabilities within picoliter sampling volumes.