Organic electrochemical transistors as novel biosensing platforms to study the electrical response of whole blood and plasma.

In this paper, for the first time to the best of our knowledge, organic electrochemical transistors are employed to investigate the electrical response of human blood, plasma and alternative buffer solutions that inhibit red blood cell (RBC) aggregation. Our focus is on selecting a suitable electrolytic platform and the related operating conditions, where the RBC effect on the OECT response can be observed separately from the strong ionic environment of plasma in whole blood. The transient response of whole blood to pulse experiments is characterized by two time constants, which can be related to blood viscosity and to the capacitive coupling between the ionic and electronic components of the overall system. The role of capacitive effects, likely due to enhanced double-layer formation by negatively charged RBCs, is also confirmed by the increase of transconductance which was found in RBC suspensions as compared to the suspending buffer. Overall, the complex behavior found in these experiments provides new insights for the development of innovative blood-based sensing devices for biomedical applications.

Layered Double Hydroxide-Based Gas Sensors for VOC Detection at Room Temperature.

Miniaturized low-cost sensors for volatile organic compounds (VOCs) have the potentiality to become a fundamental tool for indoor and outdoor air quality monitoring, to significantly improve everyday life. Layered double hydroxides (LDHs) belong to the class of anionic clays and are largely employed for NO x detection, while few results are reported on VOCs. In this work, a novel LDH coprecipitation method is proposed. For the first time, a study comparing four LDHs (ZnAl-Cl, ZnFe-Cl, ZnAl-NO3, and MgAl-NO3) is carried out to investigate the sensing performances. As explored through several microscopy and spectroscopy analyses, LDHs show a morphology characterized by a large surface area and a three-dimensional hierarchical flowerlike architecture with micro- and nanopores that induce a fast diffusion and highly effective surface interaction of the target gases. The fabricated sensors, operating at room temperature, are able to reversibly and selectively detect acetone, ethanol, ammonia, and chlorine vapors, reaching significant sensing response values up to 6% at 21 °C. The results demonstrate that by changing the LDHs' composition, it is possible to modulate the sensitivity and selectivity of the sensor, helping the discrimination of different analytes, and the consequent integration on a sensor array paves the way for electronic nose development.

Interfacing aptamers, nanoparticles and graphene in a hierarchical structure for highly selective detection of biomolecules in OECT devices.

In several biomedical applications, the detection of biomarkers demands high sensitivity, selectivity and easy-to-use devices. Organic electrochemical transistors (OECTs) represent a promising class of devices combining a minimal invasiveness and good signal transduction. However, OECTs lack of intrinsic selectivity that should be implemented by specific approaches to make them well suitable for biomedical applications. Here, we report on a biosensor in which selectivity and a high sensitivity are achieved by interfacing, in an OECT architecture, a novel gate electrode based on aptamers, Au nanoparticles and graphene hierarchically organized to optimize the final response. The fabricated biosensor performs state of the art limit of detection monitoring biomolecules, such as thrombin-with a limit of detection in the picomolar range (≤ 5 pM) and a very good selectivity even in presence of supraphysiological concentrations of Bovine Serum Albumin (BSA-1mM). These accomplishments are the final result of the gate hierarchic structure that reduces sterich indrance that could contrast the recognition events and minimizes false positive, because of the low affinity of graphene towards the physiological environment. Since our approach can be easily applied to a large variety of different biomarkers, we envisage a relevant potential for a large series of different biomedical applications.

P3HT Processing Study for In-Liquid EGOFET Biosensors: Effects of the Solvent and the Surface.

In-liquid biosensing is the new frontier of health and environment monitoring. A growing number of analytes and biomarkers of interest correlated to different diseases have been found, and the miniaturized devices belonging to the class of biosensors represent an accurate and cost-effective solution to obtaining their recognition. In this study, we investigate the effect of the solvent and of the substrate modification on thin films of organic semiconductor Poly(3-hexylthiophene) (P3HT) in order to improve the stability and electrical properties of an Electrolyte Gated Organic Field Effect Transistor (EGOFET) biosensor. The studied surface is the relevant interface between the P3HT and the electrolyte acting as gate dielectric for in-liquid detection of an analyte. Atomic Force Microscopy (AFM) and X-ray Photoelectron Spectroscopy (XPS) characterizations were employed to study the effect of two solvents (toluene and 1,2-dichlorobenzene) and of a commercial adhesion promoter (Ti Prime) on the morphological structure and electronic properties of P3HT film. Combining the results from these surface characterizations with electrical measurements, we investigate the changes on the EGOFET performances and stability in deionized (DI) water with an Ag/AgCl gate electrode.

Scaling Organic Electrochemical Transistors Down to Nanosized Channels.

The perspective of downscaling organic electrochemical transistors (OECTs) in the nanorange is approached by depositing poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) on electrodes with a nanogap designed and fabricated by electromigration induced break junction (EIBJ) technique. The electrical response of the fabricated devices is obtained by acquiring transfer characteristics in order to clarify the specific main characteristics of OECTs with sub-micrometer-sized active channels (nanogap-OECTs). On the basis of their electrical response to different scan times, the nanogap-OECT shows a maximum transconductance unaffected upon changing scan times in the time window from 1 s to 100 µs, meaning that fast varying signals can be easily acquired with unchanged amplifying performance. Hence, the scaling down of the channel size to the nanometer scale leads to a geometrical paradigm that minimizes effects on device response due to the cationic diffusion into the polymeric channel. A comprehensive study of these features is carried out by an electrochemical impedance spectroscopy (EIS) study, complemented by a quantitative analysis made by equivalent circuits. The propagation of a redox front into the polymer bulk due to ionic diffusion also known as the "intercalation pseudocapacitance" is identified as a limiting factor for the transduction dynamics.

Lift-Off Assisted Patterning of Few Layers Graphene.

Graphene and 2D materials have been exploited in a growing number of applications and the quality of the deposited layer has been found to be a critical issue for the functionality of the developed devices. Particularly, Chemical Vapor Deposition (CVD) of high quality graphene should be preserved without defects also in the subsequent processes of transferring and patterning. In this work, a lift-off assisted patterning process of Few Layer Graphene (FLG) has been developed to obtain a significant simplification of the whole transferring method and a conformal growth on micrometre size features. The process is based on the lift-off of the catalyst seed layer prior to the FLG deposition. Starting from a SiO2 finished Silicon substrate, a photolithographic step has been carried out to define the micro patterns, then an evaporation of Pt thin film on Al2O3 adhesion layer has been performed. Subsequently, the Pt/Al2O3 lift-off step has been attained using a dimethyl sulfoxide (DMSO) bath. The FLG was grown directly on the patterned Pt seed layer by Chemical Vapor Deposition (CVD). Raman spectroscopy was applied on the patterned area in order to investigate the quality of the obtained graphene. Following the novel lift-off assisted patterning technique a minimization of the de-wetting phenomenon for temperatures up to 1000 °C was achieved and micropatterns, down to 10 µm, were easily covered with a high quality FLG.

PEDOT:PSS Morphostructure and Ion-To-Electron Transduction and Amplification Mechanisms in Organic Electrochemical Transistors.

Organic electrochemical transistors (OECTs) represent a powerful and versatile type of organic-based device, widely used in biosensing and bioelectronics due to potential advantages in terms of cost, sensitivity, and system integration. The benchmark organic semiconductor they are based on is poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS), the electrical properties of which are reported to be strongly dependent on film morphology and structure. In particular, the literature demonstrates that film processing induces morphostructural changes in terms of conformational rearrangements in the PEDOT:PSS in-plane phase segregation and out-of-plane vertical separation between adjacent PEDOT-rich domains. Here, taking into account these indications, we show the thickness-dependent operation of OECTs, contextualizing it in terms of the role played by PEDOT:PSS film thickness in promoting film microstructure tuning upon controlled-atmosphere long-lasting thermal annealing (LTA). To do this, we compared the LTA-OECT response to that of OECTs with comparable channel thicknesses that were exposed to a rapid thermal annealing (RTA). We show that the LTA process on thicker films provided OECTs with an enhanced amplification capability. Conversely, on lower thicknesses, the LTA process induced a higher charge carrier modulation when the device was operated in sensing mode. The provided experimental characterization also shows how to optimize the OECT response by combining the control of the microstructure via solution processing and the effect of postdeposition processing.

Evidence of Negative Capacitance in Piezoelectric ZnO Thin Films Sputtered on Interdigital Electrodes.

The scaling paradigm known as Moore's Law, with the shrinking of transistors and their doubling on a chip every two years, is going to reach a painful end. Another less-known paradigm, the so-called Koomey's Law, stating that the computing efficiency doubles every 1.57 years, poses other important challenges, since the efficiency of rechargeable energy sources is substantially constant, and any other evolution is based on device architecture only. How can we still increase the computational power/reduce the power consumption of our electronic environments? A first answer to this question comes from the quest for new functionalities. Within this aim, negative capacitance (NC) is becoming one of the most intriguing and studied phenomena since it can be exploited for reducing the aforementioned limiting effects in the downscaling of electronic devices. Here we report the evidence of negative capacitance in 80 nm thick ZnO thin films sputtered on Au interdigital electrodes (IDEs). Highly (002)-oriented ZnO thin films, with a fine-grained surface nanostructure and the desired chemical composition, are deposited at room temperature on different IDEs structures. Direct-current electrical measurements highlighted the semiconducting nature of ZnO (current density in the order of 1 × 10(-3) A/cm(2)). When turned into the alternating current regime (from 20 Hz to 2 MHz) the presence of NC values is observed in the low-frequency range (20-120 Hz). The loss of metal/semiconductor interface charge states under forward bias conditions, together with the presence of oxygen vacancies and piezoelectric/electrostriction effects, is believed to be at the basis of the observed negative behavior, suggesting that ZnO thin-film-based field-effect transistors can be a powerful instrument to go beyond the Boltzmann limit and the downscaling of integrated circuit elements required for the fabrication of portable and miniaturized electronic devices, especially for electric household appliances working in the low 50 Hz utility frequency.