Exploring the Charge Transport of a Natural Eumelanin for Sustainable Technologies.

Eumelanin, the main quinone-based biomaterial of the melanin family of compounds, is emerging as a model for medical and sustainable electronic interfaces due to its biocompatibility, biodegradability, and transducing abilities. The study utilizes current-voltage measurements and impedance/dielectric spectroscopy under a controlled hydration atmosphere to investigate the charge transport of eumelanin produced from the S. parvus BSB49 strain. We show no differences in the electrical response in highly hydrated conditions compared to the standard synthetic eumelanin. Hence, our findings provide the groundwork to assess the potential use of this natural eumelanin in sustainable organic (bio)electronic applications.

Impact of Planar and Vertical Organic Field-Effect Transistors on Flexible Electronics.

The development of flexible and conformable devices, whose performance can be maintained while being continuously deformed, provides a significant step toward the realization of next-generation wearable and e-textile applications. Organic field-effect transistors (OFETs) are particularly interesting for flexible and lightweight products, because of their low-temperature solution processability, and the mechanical flexibility of organic materials that endows OFETs the natural compatibility with plastic and biodegradable substrates. Here, an in-depth review of two competing flexible OFET technologies, planar and vertical OFETs (POFETs and VOFETs, respectively) is provided. The electrical, mechanical, and physical properties of POFETs and VOFETs are critically discussed, with a focus on four pivotal applications (integrated logic circuits, light-emitting devices, memories, and sensors). It is pointed out that the flexible function of the relatively newer VOFET technology, along with its perspective on advancing the applicability of flexible POFETs, has not been reviewed so far, and the direct comparison regarding the performance of POFET- and VOFET-based flexible applications is most likely absent. With discussions spanning printed and wearable electronics, materials science, biotechnology, and environmental monitoring, this contribution is a clear stimulus to researchers working in these fields to engage toward the plentiful possibilities that POFETs and VOFETs offer to flexible electronics.

Room-Temperature Negative Differential Resistance in Surface-Supported Metal-Organic Framework Vertical Heterojunctions.

The advances of surface-supported metal-organic framework (SURMOF) thin-film synthesis have provided a novel strategy for effectively integrating metal-organic framework (MOF) structures into electronic devices. The considerable potential of SURMOFs for electronics results from their low cost, high versatility, and good mechanical flexibility. Here, the first observation of room-temperature negative differential resistance (NDR) in SURMOF vertical heterojunctions is reported. By employing the rolled-up nanomembrane approach, highly porous sub-15 nm thick HKUST-1 films are integrated into a functional device. The NDR is tailored by precisely controlling the relative humidity (RH) around the device and the applied electric field. The peak-to-valley current ratio (PVCR) of about two is obtained for low voltages (<2 V). A transition from a metastable state to a field emission-like tunneling is responsible for the NDR effect. The results are interpreted through band diagram analysis, density functional theory (DFT) calculations, and ab initio molecular dynamics simulations for quasisaturated water conditions. Furthermore, a low-voltage ternary inverter as a multivalued logic (MVL) application is demonstrated. These findings point out new advances in employing unprecedented physical effects in SURMOF heterojunctions, projecting these hybrid structures toward the future generation of scalable functional devices.

Enhanced Hydrophobicity in Nanocellulose-Based Materials: Toward Green Wearable Devices.

Nanocellulose is a promising material for fabricating green, biocompatible, flexible, and foldable devices. One of the main issues of using nanocellulose as a fundamental component for wearable electronics is the influence of environmental conditions on it. The water adsorption promotes the swelling of nanopaper substrates, which directly affects the devices' electrical properties prepared on/with it. Here, plant-based nanocellulose substrates, and ink composites deposited on them, are chemically modified using hexamethyldisilazane to enhance the system's hydrophobicity. After the treatment, the electrical properties of the devices exhibit stable operation under humidity levels around 95%. Such stability demonstrates that the hexamethyldisilazane modification substantially suppresses the water adsorption on fundamental device structures, namely, substrate plus conducting ink. These results attest to the robustness necessary to use nanocellulose as a key material in wearable devices such as electronic skins and tattoos and contribute to the worldwide efforts to create biodegradable devices engineered in a more deterministic fashion.

Ambipolar Resistive Switching in an Ultrathin Surface-Supported Metal-Organic Framework Vertical Heterojunction.

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.

Versatile and Robust Integrated Sensors To Locally Assess Humidity Changes in Fully Enclosed Paper-Based Devices.

The synergic combination of materials and interfaces to create novel functional devices is a crucial approach for various applications, including low-cost paper-based point-of-care systems. In this work, we demonstrate the implementation of surface-modified polypyrrole (PPy) structures, monolithically integrated into a three-dimensional multilayered paper-based microfluidic device, to locally assess humidity changes. The fabrication and integration of the system include the deterministic incorporation of PPy into the paper-based structure by gas-phase polymerization and the modification of the polymer properties to allow local humidity monitoring. The functionalization of PPy changes both the wettability and the chemical composition of the interface, what is of fundamental importance for the sensor's operation. The PPy structure has excellent mechanical stability, enduring at least 600 bending cycles, what is of relevance on flexible electronics. The electrical resistance correlates with the local relative humidity (RH) inside of the sealed microfluidic system, and the sensor response is fully reversible. The integrated system capable of locally monitoring the RH allowed us to verify that inside the microfluidic channel, water molecules can diffuse across the wax barriers-a possibility disregarded so far. Our results attest that RH variations of 5-10% can affect the flow of extended channels (>5 cm) even when they are fully enclosed.

Deposition of exchange-coupled dinickel complexes on gold substrates utilizing ambidentate mercapto-carboxylato ligands.

The chemisorption of magnetically bistable transition metal complexes on planar surfaces has recently attracted increased scientific interest due to its potential application in various fields, including molecular spintronics. In this work, the synthesis of mixed-ligand complexes of the type [NiII2L(L')](ClO4), where L represents a 24-membered macrocyclic hexaazadithiophenolate ligand and L' is a ω-mercapto-carboxylato ligand (L' = HS(CH2)5CO2- (6), HS(CH2)10CO2- (7), or HS(C6H4)2CO2- (8)), and their ability to adsorb on gold surfaces is reported. Besides elemental analysis, IR spectroscopy, electrospray ionization mass spectrometry (ESIMS), UV-vis spectroscopy, and X-ray crystallography (for 6 and 7), the compounds were also studied by temperature-dependent magnetic susceptibility measurements (for 7 and 8) and (broken symmetry) density functional theory (DFT) calculations. An S = 2 ground state is demonstrated by temperature-dependent susceptibility and magnetization measurements, achieved by ferromagnetic coupling between the spins of the Ni(II) ions in 7 (J = +22.3 cm-1) and 8 (J = +20.8 cm-1; H = -2JS1S2). The reactivity of complexes 6-8 is reminiscent of that of pure thiolato ligands, which readily chemisorb on Au surfaces as verified by contact angle, atomic force microscopy (AFM) and spectroscopic ellipsometry measurements. The large [Ni2L] tail groups, however, prevent the packing and self-assembly of the hydrocarbon chains. The smaller film thickness of 7 is attributed to the specific coordination mode of the coligand. Results of preliminary transport measurements utilizing rolled-up devices are also reported.

Flexible and Foldable Fully-Printed Carbon Black Conductive Nanostructures on Paper for High-Performance Electronic, Electrochemical, and Wearable Devices.

In this work, we demonstrate the first example of fully printed carbon nanomaterials on paper with unique features, aiming the fabrication of functional electronic and electrochemical devices. Bare and modified inks were prepared by combining carbon black and cellulose acetate to achieve high-performance conductive tracks with low sheet resistance. The carbon black tracks withstand extremely high folding cycles (>20 000 cycles), a new record-high with a response loss of less than 10%. The conductive tracks can also be used as 3D paper-based electrochemical cells with high heterogeneous rate constants, a feature that opens a myriad of electrochemical applications. As a relevant demonstrator, the conductive ink modified with Prussian-blue was electrochemically characterized proving to be very promising toward the detection of hydrogen peroxide at very low potentials. Moreover, carbon black circuits can be fully crumpled with negligible change in their electrical response. Fully printed motion and wearable sensors are additional examples where bioinspired microcracks are created on the conductive track. The wearable devices are capable of efficiently monitoring extremely low bending angles including human motions, fingers, and forearm. Here, to the best of our knowledge, the mechanical, electronic, and electrochemical performance of the proposed devices surpasses the most recent advances in paper-based devices.

Direct Drawing Method of Graphite onto Paper for High-Performance Flexible Electrochemical Sensors.

A simple and fast fabrication method to create high-performance pencil-drawn electrochemical sensors is reported for the first time. The sluggish electron transfer observed on bare pencil-drawn surfaces was enhanced using two electrochemical steps: first oxidizing the surface and then reducing it in a subsequent step. The heterogeneous rate constant was found to be 5.1 × 10-3 cm s-1, which is the highest value reported so far for pencil-drawn surfaces. We mapped the origin of such performance by atomic force microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy. Our results suggest that the oxidation process leads to chemical and structural transformations on the electrode surface. As a proof-of-concept, we modified the pencil-drawn surface with Meldola's blue to electrocatalytically detect nicotinamide adenine dinucleotide (NADH). The electrochemical device exhibited the highest catalytic constant (1.7 × 105 L mol-1 s-1) and the lowest detection potential for NADH reported so far in paper-based electrodes.

A simple capacitive method to evaluate ethanol fuel samples.

Ethanol is a biofuel used worldwide. However, the presence of excessive water either during the distillation process or by fraudulent adulteration is a major concern in the use of ethanol fuel. High water levels may cause engine malfunction, in addition to being considered illegal. Here, we describe the development of a simple, fast and accurate platform based on nanostructured sensors to evaluate ethanol samples. The device fabrication is facile, based on standard microfabrication and thin-film deposition methods. The sensor operation relies on capacitance measurements employing a parallel plate capacitor containing a conformational aluminum oxide (Al2O3) thin layer (15 nm). The sensor operates over the full range water concentration, i.e., from approximately 0% to 100% vol. of water in ethanol, with water traces being detectable down to 0.5% vol. These characteristics make the proposed device unique with respect to other platforms. Finally, the good agreement between the sensor response and analyses performed by gas chromatography of ethanol biofuel endorses the accuracy of the proposed method. Due to the full operation range, the reported sensor has the technological potential for use as a point-of-care analytical tool at gas stations or in the chemical, pharmaceutical, and beverage industries, to mention a few.

Three-Dimensional Organic Conductive Networks Embedded in Paper for Flexible and Foldable Devices.

The fabrication of three-dimensional (3D) polypyrrole conductive tracks through the porous structure of paper is demonstrated by the first time. We combined paper microfluidics and gas-phase pyrrole monomers to chemically synthesize polypyrrole-conducting channels embedded in-between the cellulose fibers. By using this method, foldable conductive structures can be created across the whole paper structure, allowing the electrical connection between both sides of the substrate. As a proof of concept, top-channel-top (TCT) and top-channel-bottom (TCB) conductive interconnections as well as all-organic paper-based touch buttons are demonstrated.