Ultrahigh-Gain Organic Electrochemical Transistor Chemosensors Based on Self-Curled Nanomembranes.

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.

Temperature-Independent Polarization of Ultrathin Phthalocyanine-Based Hybrid Organic/Inorganic Heterojunctions.

The combination of organic and inorganic materials at the nanoscale to form functional hybrid structures is a powerful strategy to develop novel electronic devices. The knowledge on semiconductor thin-film polarization brings direct benefits to the hybrid organic/inorganic electronics, becoming primordial for the development of devices such as electromechanical logic gates, solar cells, miniaturized valves, organic diodes, and molecular supercapacitors, among others. Here, we report on the dielectric polarization of ultrathin organic semiconducting films-ca. 5 nm thick metal phthalocyanine ensembles (viz., CuPc, CoPc, F16CuPc)-employed to build up hybrid metal/oxide/molecule heterojunctions. Such hybrid heterostructures are fully integrated into self-rolled nanomembrane-based capacitors and further investigated by impedance spectroscopy measurements as a function of temperature (from 6 to 300 K). The dielectric polarization of the metal phthalocyanines is found to be thermally activated above a specific threshold temperature, which depends on the molecular structure. Below this threshold, the current leakage across the system is suppressed, thus evidencing intrinsic-like polarization mechanisms. The temperature-independent permittivities of the ultrathin molecular films are found to be strongly dependent on the organic/inorganic hybrid interfaces, while the calculated relaxation times are more likely related to each single-molecule polarization. Beyond the advances in determining the temperature dependence of the permittivity for ultrathin phthalocyanine films integrated within solid-state electronics, our results also support the deterministic design of novel functional devices based on nanoscale hybrid organic/inorganic heterojunctions.

Edge-driven nanomembrane-based vertical organic transistors showing a multi-sensing capability.

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.

Low-Voltage, Flexible, and Self-Encapsulated Ultracompact Organic Thin-Film Transistors Based on Nanomembranes.

Organic thin-film transistors (OTFTs) are an ever-growing subject of research, powering recent technologies such as flexible and wearable electronics. Currently, many studies are being carried out to push forward the state-of-the-art OTFT technology to achieve characteristics that include high carrier mobility, low power consumption, flexibility, and the ability to operate under harsh conditions. Here, we tackle this task by proposing a novel OTFT architecture exploring the so-called rolled-up nanomembrane technology to fabricate low-voltage (<2 V), ultracompact OTFTs. As the OTFT gate electrode, we use strained nanomembranes, which allows all transistor components to be rolled-up and confined into a tubular-shaped tridimensional device structure with reduced footprint (ca. 90% of their planar counterpart), without any loss of electrical performance. Such an innovative architecture endows the OTFTs high mechanical flexibility (bending radius of <30 µm) and robustness-the devices can be reversibly deformed, withstanding more than 500 radial compression/decompression cycles. Additionally, the tubular device design possesses an inherent self-encapsulation characteristic that protects the OTFT active region from degradation by UV-light and hazardous vapors. The reported strategy is also shown to be compatible with different organic semiconductor materials. All of these characteristics contribute to further extending the potentialities of OTFTs, mainly toward rugged electronics.

Hybrid nanomembrane-based capacitors for the determination of the dielectric constant of semiconducting molecular ensembles.

Considerable advances in the field of molecular electronics have been achieved over the recent years. One persistent challenge, however, is the exploitation of the electronic properties of molecules fully integrated into devices. Typically, the molecular electronic properties are investigated using sophisticated techniques incompatible with a practical device technology, such as the scanning tunneling microscopy. The incorporation of molecular materials in devices is not a trivial task as the typical dimensions of electrical contacts are much larger than the molecular ones. To tackle this issue, we report on hybrid capacitors using mechanically-compliant nanomembranes to encapsulate ultrathin molecular ensembles for the investigation of molecular dielectric properties. As the prototype material, copper (II) phthalocyanine (CuPc) has been chosen as information on its dielectric constant (k CuPc) at the molecular scale is missing. Here, hybrid nanomembrane-based capacitors containing metallic nanomembranes, insulating Al2O3 layers, and the CuPc molecular ensembles have been fabricated and evaluated. The Al2O3 is used to prevent short circuits through the capacitor plates as the molecular layer is considerably thin (<30 nm). From the electrical measurements of devices with molecular layers of different thicknesses, the CuPc dielectric constant has been reliably determined (k CuPc = 4.5 ± 0.5). These values suggest a mild contribution of the molecular orientation on the CuPc dielectric properties. The reported nanomembrane-based capacitor is a viable strategy for the dielectric characterization of ultrathin molecular ensembles integrated into a practical, real device technology.

Hybrid organic/inorganic interfaces as reversible label-free platform for direct monitoring of biochemical interactions.

The combination of organic and inorganic materials to create hybrid nanostructures is an effective approach to develop label-free platforms for biosensing as well as to overcome eventual leakage current-related problems in capacitive sensors operating in liquid. In this work, we combine an ultra-thin high-k dielectric layer (Al2O3) with a nanostructured organic functional tail to create a platform capable of monitoring biospecific interactions directly in liquid at very low analyte concentrations. As a proof of concept, a reversible label-free glutathione-S-transferase (GST) biosensor is demonstrated. The sensor can quantify the GST enzyme concentration through its biospecific interaction with tripeptide reduced glutathione (GSH) bioreceptor directly immobilized on the dielectric surface. The enzymatic reaction is monitored by electrical impedance measurements, evaluating variations on the overall capacitance values according to the GST concentration. The biosensor surface can be easily regenerated, allowing the detection of GST with the very same device. The biosensor shows a linear response in the range of 200pmolL-1 to 2µmolL-1, the largest reported in the literature along with the lowest detectable GST concentration (200pmolL-1) for GST label-free sensors. Such a nanostructured hybrid organic-inorganic system represents a powerful tool for the monitoring of biochemical reactions, such as protein-protein interactions, for biosensing and biotechnological applications.