Fabio Cicoira

Influence of Device Geometry on Sensor Characteristics of Planar Organic Electrochemical Transistors

The response of PEDOT:PSS planar electrochemical transistors to H2O2 can be tuned by varying the ratio between the areas of the channel and the gate electrode. Devices with small gates show lower background signal and higher sensitivity. The detection range, on the other hand, is found to be rather independent of the gate/channel area ratio.

Step-by-step growth of epitaxially aligned polythiophene by surface-confined reaction

One of the great challenges in surface chemistry is to assemble aromatic building blocks into ordered structures that are mechanically robust and electronically interlinked—i.e., are held together by covalent bonds. We demonstrate the surface-confined growth of ordered arrays of poly(3,4-ethylenedioxythiophene) (PEDOT) chains, by using the substrate (the 110 facet of copper) simultaneously as template and catalyst for polymerization. Copper acts as promoter for the Ullmann coupling reaction, whereas the inherent anisotropy of the fcc 110 facet confines growth to a single dimension. High resolution scanning tunneling microscopy performed under ultrahigh vacuum conditions allows us to simultaneously image PEDOT oligomers and the copper lattice with atomic resolution. Density functional theory calculations confirm an unexpected adsorption geometry of the PEDOT oligomers, which stand on the sulfur atom of the thiophene ring rather than lying flat. This polymerization approach can be extended to many other halogen-terminated molecules to produce epitaxially aligned conjugated polymers. Such systems might be of central importance to develop future electronic and optoelectronic devices with high quality active materials, besides representing model systems for basic science investigations.

Melanins and melanogenesis: from pigment cells to human health and technological applications

During the past decade, melanins and melanogenesis have attracted growing interest for a broad range of biomedical and technological applications. The burst of polydopamine‐based multifunctional coatings in materials science is just one example, and the list may be expanded to include melanin thin films for organic electronics and bioelectronics, drug delivery systems, functional nanoparticles and biointerfaces, sunscreens, environmental remediation devices. Despite considerable advances, applied research on melanins and melanogenesis is still far from being mature. A closer intersectoral interaction between research centers is essential to raise the interests and increase the awareness of the biomedical, biomaterials science and hi‐tech sectors of the manifold opportunities offered by pigment cells and related metabolic pathways. Starting from a survey of biological roles and functions, the present review aims at providing an interdisciplinary perspective of melanin pigments and related pathway with a view to showing how it is possible to translate current knowledge about physical and chemical properties and control mechanisms into new bioinspired solutions for biomedical, dermocosmetic, and technological applications.

Tetracene light-emitting transistors on flexible plastic substrates

We report on organic light-emitting (field-effect) transistors (LETs) fabricated on a flexible and transparent plastic foil (Mylar), acting both as substrate and gate dielectric. The foil is patterned on one side with bottom-contact gold source and drain electrodes, while a thin film of gold is evaporated on the opposite side of the foil to form the gate electrode. A vacuum sublimed tetracene film is employed as an active layer for charge transport and light emission. Atomic force microscopy shows that tetracene films have a good adhesion on Mylar and exhibit a granular structure. The transistor shows unipolar p-type behavior with mobilities typically of 5×10−4cm2∕Vs. Drain-source current and electroluminescence have been simultaneously measured. Provided a suitable gate bias is applied, light emission occurs at drain-source voltages (Vds) above saturation. LETs on plastic substrates could open the way to flexible devices combining the switching function of a transistor and the light emission.

Effect of the gate electrode on the response of organic electrochemical transistors

Organic electrochemical transistors (OECTs) are attracting a great deal of interest for biosensing and bioelectronics applications. However, their device physics is not yet well-understood. In this paper, we focus on the effect of the gate electrode material on the response of OECTs. We studied OECTs made from the conducting polymer poly(3,4-ethylenedioxythiophene) doped with poly(styrene sulfonate), and which utilized halide electrolytes. We demonstrate that OECTs with Ag gate electrodes show larger current modulation compared to OECTs with Pt gate electrodes. This effect is due to a change in the OECT regime of operation from capacitive, in case of a Pt gate electrode, to Faradaic, in the case of an Ag electrode.

New opportunities for organic electronics and bioelectronics: ions in action

This perspective deals with the coupling of ionic and electronic transport in organic electronic devices, focusing on electrolyte-gated transistors. These include electrolyte-gated organic field-effect transistors (EG-OFETs) and organic electrochemical transistors (OECTs). EG-OFETs, based on molecules and polymers, can be operated at low electrical bias (about 1 V or below) and permit unprecedented charge carrier densities within the transistor channel. OECTs can be operated in aqueous environment as efficient ion-to-electron converters, thus providing an interface between the worlds of biology and electronics. The exploration and the exploitation of coupled ionic and electronic transport in organic materials brings together different disciplines such as materials science, physics, chemistry, electrochemistry, organic electronics and biology.

Decreasing surface outgassing by thin film getter coatings

Abstract The UHV behaviour of stainless steel vacuum chambers, coated ex situ by sputtering with a thin film of a getter material, has been investigated. The purpose of this study was to ascertain if the getter film could be activated after air exposure by in situ baking, so as to transform the vacuum chamber from a gas source into a pump. Many elements and alloys have been tested, all of which could be activated by baking at temperatures acceptable for stainless steel components, i.e. lower than 400 °C. In one case (equiatomic TiZr alloy) an activation temperature of 200–250 °C has been measured. This investigation has been carried out using Electron Stimulated Desorption, pumping speed and ultimate pressure measurements.

Nonevaporable getter films for ultrahigh vacuum applications

The vacuum behavior of stainless steel vacuum chambers, ex situ sputter coated with a thin film (∼1 μm) of getter material, has been studied to determine if after air exposure the getter film could be activated by a bakeout so as to transform the coated vacuum chamber into a pump. The materials studied so far are Ti, Zr, Hf, and some of their binary alloys. They all display an activation temperature lower than 400 °C, i.e., within the reach of the baking temperature of stainless steel vacuum chambers. The lowest activation temperature of 200–250 °C, measured for an equiatomic alloy of Ti and Zr, allows extension of this method to chambers made of copper and aluminum alloys. The experimental results, described here in detail, indicate that the values of the activation temperature obtained using electron stimulated desorption, pumping speed, and Auger spectroscopy measurements are self-consistent.

Ambipolar copper phthalocyanine transistors with carbon nanotube array electrodes

We report on organic thin film transistors (OTFTs) based on copper phthalocyanine (CuPc) having electrodes consisting of isolated carbon nanotube (CNT) arrays embedded in the organic layer. CuPc OTFT with CNT array electrodes show p-type behavior with Ohmic hole injection, high hole mobility, and enhanced switching characteristics at low voltage. The p-type devices are converted to ambipolar OTFT by vacuum annealing. Despite the large offset between the CNT work function and the CuPc energy levels, electron injection characteristics are also Ohmic. The extension of CNT electrodes to the phthalocyanine family confirms the validity of this contact approach for organic electronic devices.

Making Contacts to n-Type Organic Transistors Using Carbon Nanotube Arrays

We investigated the performance of carbon nanotube (CNT) array electrodes applied to n-type and ambipolar phenyl-C61-butyric acid methyl ester (PCBM) thin film transistors on a SiO(2) dielectric substrate. Compared to conventional Au electrodes, CNT arrays provide better injection efficiency, improved switching behavior, higher electron mobility, and lower contact resistance. Experiments on ambipolar PCBM transistors indicate that the injection performance is enhanced by the electrostatics of the CNT contacts, which promotes electron and hole tunneling across Schottky barriers at the PCBM/nanotube interface. The use of CNT arrays is a valid replacement to low workfunction metals, which are often reactive in air and difficult to process. Our work paves the way for a widespread use of carbon nanotube array electrodes in high-performance n-type and p-type organic thin film transistors.