Francesca Leonardi

Ambipolar Multi‐Stripe Organic Field‐Effect Transistors

Among these, the exploitation of sensing capabilities has recently been a focus of major interest because of OFETs versatility, low costs and their integration with microfl uidics. In the simplest confi guration of OFETs sensor, the direct electrical detection of analytes is produced by the fi eld-effect modulation of the conductivity of the organic semiconductor layer due to interaction of the semiconductor with the analytes or with the light. The possibility of building arrays of OFETs, each bearing a different active material, allows the detection and identifi cation of a variety of substances in solution as well as in the gas phase. [ 15 ]

Multiscale Sensing of Antibody - Antigen Interactions by Organic Transistors and Single-Molecule Force Spectroscopy

Antibody-antigen (Ab-Ag) recognition is the primary event at the basis of many biosensing platforms. In label-free biosensors, these events occurring at solid-liquid interfaces are complex and often difficult to control technologically across the smallest length scales down to the molecular scale. Here a molecular-scale technique, such as single-molecule force spectroscopy, is performed across areas of a real electrode functionalized for the immunodetection of an inflammatory cytokine, viz. interleukin-4 (IL4). The statistical analysis of force-distance curves allows us to quantify the probability, the characteristic length scales, the adhesion energy, and the time scales of specific recognition. These results enable us to rationalize the response of an electrolyte-gated organic field-effect transistor (EGOFET) operated as an IL4 immunosensor. Two different strategies for the immobilization of IL4 antibodies on the Au gate electrode have been compared: antibodies are bound to (i) a smooth film of His-tagged protein G (PG)/Au; (ii) a 6-aminohexanethiol (HSC6NH2) self-assembled monolayer on Au through glutaraldehyde. The most sensitive EGOFET (concentration minimum detection level down to 5 nM of IL4) is obtained with the first functionalization strategy. This result is correlated to the highest probability (30%) of specific binding events detected by force spectroscopy on Ab/PG/Au electrodes, compared to 10% probability on electrodes with the second functionalization. Specifically, this demonstrates that Ab/PG/Au yields the largest areal density of oriented antibodies available for recognition. More in general, this work shows that specific recognition events in multiscale biosensors can be assessed, quantified, and optimized by means of a nanoscale technique.

Double layer capacitance measured by organic field effect transistor operated in water

Pentacene ultra thin film transistors were exposed to water and operated with a conventional silicon/silicon oxide bottom gate and an electrolyte top gate controlled by a working electrode. The transistors are highly sensible (µV) to the electrochemical potential of the aqueous electrolyte. We show that dual gate operation permits the measurement of the double layer capacitance, CDL = 14.6 µF/cm2. The device exhibits a fast (4.6 ms) and stable response, without bias stress as opposed to conventional bottom gate operations, when controlled with the electrolyte gate. These features make the device a promising candidate for potentiometric transducers required for non-invasive electrophysiology.

Electrochemical Functionalization of Graphene at the Nanoscale with Self-Assembling Diazonium Salts

We describe a fast and versatile method to functionalize high-quality graphene with organic molecules by exploiting the synergistic effect of supramolecular and covalent chemistry. With this goal, we designed and synthesized molecules comprising a long aliphatic chain and an aryl diazonium salt. Thanks to the long chain, these molecules physisorb from solution onto CVD graphene or bulk graphite, self-assembling in an ordered monolayer. The sample is successively transferred into an aqueous electrolyte, to block any reorganization or desorption of the monolayer. An electrochemical impulse is used to transform the diazonium group into a radical capable of grafting covalently to the substrate and transforming the physisorption into a covalent chemisorption. During covalent grafting in water, the molecules retain the ordered packing formed upon self-assembly. Our two-step approach is characterized by the independent control over the processes of immobilization of molecules on the substrate and their covalent tethering, enabling fast (t < 10 s) covalent functionalization of graphene. This strategy is highly versatile and works with many carbon-based materials including graphene deposited on silicon, plastic, and quartz as well as highly oriented pyrolytic graphite.

Logic-gate devices based on printed polymer semiconducting nanostripes.

The applications of organic semiconductors in complex circuitry such as printed CMOS-like logic circuits demand miniaturization of the active structures to the submicrometric and nanoscale level while enhancing or at least preserving the charge transport properties upon processing. Here, we addressed this issue by using a wet lithographic technique, which exploits and enhances the molecular order in polymers by spatial confinement, to fabricate ambipolar organic field effect transistors and inverter circuits based on nanostructured single component ambipolar polymeric semiconductor. In our devices, the current flows through a precisely defined array of nanostripes made of a highly ordered diketopyrrolopyrrole-benzothiadiazole copolymer with high charge carrier mobility (1.45 cm(2) V(-1) s(-1) for electrons and 0.70 cm(2) V(-1) s(-1) for holes). Finally, we demonstrated the functionality of the ambipolar nanostripe transistors by assembling them into an inverter circuit that exhibits a gain (105) comparable to inverters based on single crystal semiconductors.

Patterned conductive nanostructures from reversible self-assembly of 1D coordination polymer

In this study, the outstanding ability of the coordination polymer [Pt2(nBuCS2)4I]n (nBu = n-butyl) (1) to reversibly self-organize from solution was demonstrated. This feature allowed us to generate highly electrical conductive structures located upon demand on technologically relevant surfaces, by easy-to-handle and low cost micromolding in capillaries (MIMIC) and lithographically controlled wetting (LCW). Electrical characterization reveals a near Ohmic behaviour and a high stability of the stripes (in air). Electrodes produced by the MIMIC technique from a solution of compound 1 demonstrated that this material can be efficiently used as electrodes for organic field-effect transistors (OFETs).

Targeting ordered oligothiophene fibers with enhanced functional properties by interplay of self-assembly and wet lithography

Reproducible spatial control of a self-assembly process of fiber-forming oligothiophenes was achieved by using confinement effects. This strategy allowed the direct integration with a precise control over density, orientation, and size of supramolecular semiconducting fibers in OFET devices, demonstrating that well-aligned fibers exhibit a substantial enhancement of electrical performances.

Mono/bidentate thiol oligoarylene-based self-assembled monolayers (SAMs) for interface engineering

A new set of linear oligoarylene thiol molecules, namely (4′-(Thiophen-2-yl)Biphenyl-3,5-diyl)Dimethanethiol (TBD), (4′-(Thiophen-2-yl)Biphenyl-4-yl)Methanethiol (TBM) and ([1,1′;4′,1′′]Terphenyl-3,5-diyl)Dimethanethiol (TD), were synthesized and used for functionalizing the polycrystalline gold electrodes. Such molecules differ for the number of anchoring groups (TBM vs. TBD) and the terminal rings (TD vs. TBD). As shown by electrochemical measurements, they form homogeneous and pinholes-free self-assembly monolayers (SAMs) when deposited on the gold electrode. Moreover, the wettability of the functionalized surface and the morphological changes of pentacene films grown on SAMs were investigated by contact angle and atomic force microscopy, respectively. OTFT has been used as organic gauge for investigating the metal–SAM–organic semiconductor structure. Charge carriers mobility, threshold voltage, contact resistance were measured in both air and vacuum to assess the influence of the anchoring groups and the terminal rings to the transistor performance. Although these SAMs do not show an improvement of mobility due to an increase of contact resistance, they allow a better modulation of the current flowing across the electrode–organic semiconductor (OS) interface, pointing out the structural differences between the three SAMs in terms of resistance drop combined with the critical voltage.

High performing solution-coated electrolyte-gated organic field-effect transistors for aqueous media operation

Since the first demonstration, the electrolyte-gated organic field-effect transistors (EGOFETs) have immediately gained much attention for the development of cutting-edge technology and they are expected to have a strong impact in the field of (bio-)sensors. However EGOFETs directly expose their active material towards the aqueous media, hence a limited library of organic semiconductors is actually suitable. By using two mostly unexplored strategies in EGOFETs such as blended materials together with a printing technique, we have successfully widened this library. Our benchmarks were 6,13-bis(triisopropylsilylethynyl)pentacene and 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene (diF-TES-ADT), which have been firstly blended with polystyrene and secondly deposited by means of the bar-assisted meniscus shearing (BAMS) technique. Our approach yielded thin films (i.e. no thicker than 30 nm) suitable for organic electronics and stable in liquid environment. Up to date, these EGOFETs show unprecedented performances. Furthermore, an extremely harsh environment, like NaCl 1M, has been used in order to test the limit of operability of these electronic devices. Albeit an electrical worsening is observed, our devices can operate under different electrical stresses within the time frame of hours up to a week. In conclusion, our approach turns out to be a powerful tool for the EGOFET manufacturing.

Electrochemical Fabrication of Surface Chemical Gradients in Thiol Self-Assembled Monolayers with Tailored Work-Functions

The studies on surface chemical gradients are constantly gaining interest both for fundamental studies and for technological implications in materials science, nanofluidics, dewetting, and biological systems. Here we report on a new approach that is very simple and very efficient, to fabricate surface chemical gradients of alkanethiols, which combines electrochemical desorption/partial readsorption, with the withdrawal of the surface from the solution. The gradient is then stabilized by adding a complementary thiol terminated with a hydroxyl group with a chain length comparable to desorbed thiols. This procedure allows us to fabricate a chemical gradient of the wetting properties and the substrate work-function along a few centimeters with a gradient slope higher than 5°/cm. Samples were characterized by cyclic voltammetry during desorption, static contact angle, XPS analysis, and Kelvin probe. Computer simulations based on the Dissipative Particle Dynamics methods were carried out considering a water droplet on a mixed SAM surface. The results help to rationalize the composition of the chemical gradient at different position on the Au surface.