Kyriaki Manoli

Tailoring Functional Interlayers in Organic Field‐Effect Transistor Biosensors

This review aims to provide an update on the development involving dielectric/organic semiconductor (OSC) interfaces for the realization of biofunctional organic field-effect transistors (OFETs). Specific focus is given on biointerfaces and recent technological approaches where biological materials serve as interlayers in back-gated OFETs for biosensing applications. Initially, to better understand the effects produced by the presence of biomolecules deposited at the dielectric/OSC interfacial region, the tuning of the dielectric surface properties by means of self-assembled monolayers is discussed. Afterward, emphasis is given to the modification of solid-state dielectric surfaces, in particular inorganic dielectrics, with biological molecules such as peptides and proteins. Special attention is paid on how the presence of an interlayer of biomolecules and bioreceptors underneath the OSC impacts on the charge transport and sensing performance of the device. Moreover, naturally occurring materials, such as carbohydrates and DNA, used directly as bulk gating materials in OFETs are reviewed. The role of metal contact/OSC interface in the overall performance of OFET-based sensors is also discussed.

Printable Bioelectronics To Investigate Functional Biological Interfaces

Thin-film transistors can be used as high-performance bioelectronic devices to accomplish tasks such as sensing or controlling the release of biological species as well as transducing the electrical activity of cells or even organs, such as the brain. Organic, graphene, or zinc oxide are used as convenient printable semiconducting layers and can lead to high-performance low-cost bioelectronic sensing devices that are potentially very useful for point-of-care applications. Among others, electrolyte-gated transistors are of interest as they can be operated as capacitance-modulated devices, because of the high capacitance of their charge double layers. Specifically, it is the capacitance of the biolayer, being lowest in a series of capacitors, which controls the output current of the device. Such an occurrence allows for extremely high sensitivity towards very weak interactions. All the aspects governing these processes are reviewed here.

Printable and flexible electronics: From TFTs to bioelectronic devices

Printable and flexible thin-film transistors (TFTs) have gained significant attention over the last few years thanks to their implementation in many different sectors. Beside applications in large-area electronics such as flat displays, sensors and radio frequency identification tags, these devices have been widely investigated for life sciences applications too, including label-free biosensors, systems for drug delivery and implantable platforms. This review highlights the recent advances in the field of highly performing low-cost TFT devices realized by printing or printing compatible technologies and suitable for bioelectronics applications. Novel printable materials used as semiconductors, dielectrics and electrodes as well as printing technologies useful for the realization of the elicited devices are discussed as well. Particularly attention is given to printing techniques employed for the deposition of biological materials and to methods for realizing label-free electronic biosensors.

Plain Poly(acrylic acid) Gated Organic Field-Effect Transistors on a Flexible Substrate

We report on the use of a polyanionic proton conductor, poly(acrylic acid), to gate a poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene]-based organic field-effect transistor (OFET). A planar configuration of the OFET is evaluated, and the electrical performance and implementation on a flexible substrate are discussed.

A comparative study of the gas sensing behavior in P3HT- and PBTTT-based OTFTs: the influence of film morphology and contact electrode position.

Bottom- and top-contact organic thin film transistors (OTFTs) were fabricated, using poly(3-hexylthiophene-2,5-diyl) (P3HT) and poly[2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene] (PBTTT-C16) as p-type channel semiconductors. Four different types of OTFTs were fabricated and investigated as gas sensors against three volatile organic compounds, with different associated dipole moments. The OTFT-based sensor responses were evaluated with static and transient current measurements. A comparison between the different architectures and the relative organic semiconductor was made.

Organic bioelectronics probing conformational changes in surface confined proteins

The study of proteins confined on a surface has attracted a great deal of attention due to its relevance in the development of bio-systems for laboratory and clinical settings. In this respect, organic bio-electronic platforms can be used as tools to achieve a deeper understanding of the processes involving protein interfaces. In this work, biotin-binding proteins have been integrated in two different organic thin-film transistor (TFT) configurations to separately address the changes occurring in the protein-ligand complex morphology and dipole moment. This has been achieved by decoupling the output current change upon binding, taken as the transducing signal, into its component figures of merit. In particular, the threshold voltage is related to the protein dipole moment, while the field-effect mobility is associated with conformational changes occurring in the proteins of the layer when ligand binding occurs. Molecular Dynamics simulations on the whole avidin tetramer in presence and absence of ligands were carried out, to evaluate how the tight interactions with the ligand affect the protein dipole moment and the conformation of the loops surrounding the binding pocket. These simulations allow assembling a rather complete picture of the studied interaction processes and support the interpretation of the experimental results.

UV crosslinked poly(acrylic acid): a simple method to bio-functionalize electrolyte-gated OFET biosensors

A simple and time-saving wet method to endow the surface of organic semiconductor films with carboxyl functional groups is presented. A thin layer of poly(acrylic acid) (pAA) is spin-coated directly on the electronic channel of an electrolyte-gated organic FET (EGOFET) device and cross-linked by UV exposure without the need for any photo-initiator. The carboxyl functionalities are used to anchor phospholipid bilayers through the reaction with the amino-groups of phosphatidyl-ethanolamine (PE). By loading the membranes with phospholipids carrying specific functionalities, such a platform can be easily implemented with recognition elements. Here the case of biotinylated phospholipids that allow selective streptavidin electronic detection is described. The surface morphology and chemical composition are monitored using SEM and XPS, respectively, during the whole process of bio-functionalization. The electronic and sensing performance level of the EGOFET biosensing platform is also evaluated. Selective analyte (streptavidin) detection in the low pM range is achieved, this being orders of magnitude lower than the performance level obtained by the well assessed surface plasmon resonance assay reaching the nM level, at most.

Effect of the gate metal work function on water-gated ZnO thin-film transistor performance

ZnO thin films, prepared using a printing-compatible sol–gel method involving a thermal treatment below 400 °C, are proposed as active layers in water-gated thin-film transistors (WG-TFTs). The thin-film structure and surface morphology reveal the presence of contiguous ZnO crystalline (hexagonal wurtzite) with isotropic nano-grains as large as 10 nm characterized by a preferential orientation along the a-axis. The TFT devices are gated through a droplet of deionized water by means of electrodes characterized by different work functions. The high capacitance of the electrolyte allowed operation below 0.5 V. While the Ni, Pd, Au and Pt gate electrodes are electrochemically stable in the inspected potential range, electrochemical activity is revealed for the W one. Such an occurrence leads to an increase of capacitance (and current), which is ascribed to a high output current from the dissolution of a lower capacitance W-oxide layer. The environmental stability of the ZnO WG-TFTs is quite good over a period of five months.

A hydrogel capsule as gate dielectric in flexible organic field-effect transistors

A jellified alginate based capsule serves as biocompatible and biodegradable electrolyte system to gate an organic field-effect transistor fabricated on a flexible substrate. Such a system allows operating thiophene based polymer transistors below 0.5 V through an electrical double layer formed across an ion-permeable polymeric electrolyte. Moreover, biological macro-molecules such as glucose-oxidase and streptavidin can enter into the gating capsules that serve also as delivery system. An enzymatic bio-reaction is shown to take place in the capsule and preliminary results on the measurement of the electronic responses promise for low-cost, low-power, flexible electronic bio-sensing applications using capsule-gated organic field-effect transistors.

The double layer capacitance of ionic liquids for electrolyte gating of ZnO thin film transistors and effect of gate electrodes

Electrolyte gated thin film transistors (TFTs) based on sol–gel processed zinc oxide (ZnO) are investigated using imidazolium-based ionic liquids (ILs), namely [bmim][BF4] and [bmim][PF6], as electrolytes. The capacitance of the ILs is determined by means of electrochemical impedance spectroscopy. The frequency dependence of the capacitance measurements indicates that the electric double layers (EDLs) form below 1 kHz. Impedance measurements are also acquired at different gate voltages and the effect of the bias is discussed in detail. The experimental data suggest that the double layer capacitance of the two ILs depends on the polarization voltage. In terms of transistor characteristics, minimum hysteresis is observed in the case of [bmim][BF4]. Being smaller in size out of the two, a higher ionic mobility is expected. Therefore, faster formation of the EDL can account for suppressed hysteresis in the I–V characteristics. The estimated capacitance was 1.17 μF cm−2 for [bmim][PF6] and 4.05 μF cm−2 for [bmim][BF4], which resulted in a TFT field-effect mobility as high as 6.0 and 1.4 cm2 V−1 s−1, respectively. Also the on–off ratio of the EG-TFT is particularly high, being 104. Moreover, transient current measurements showed that the two ILs behave differently under continuous bias stress. The effect of the metal gate electrode on the device characteristics is also investigated. Five metals of varying work functions are employed for establishing a gate/IL interface. The data do not support that there is a correlation between the threshold voltage and the work function of the metals. On the other hand, the capacitance seems to be more susceptible to changes of the metal gate.