A nanoscale study of the structure and electrical response of Sepia eumelanin.

Eumelanin, the brown-black member of the melanin biopigment family, is a prototype material for sustainable (green) organic electronics. Sepia eumelanin (Sepia) is a type of biosourced eumelanin extracted from the ink sac of cuttlefish. Electron microscopy and scanning probe microscopy images of Sepia show distinguishable near spherical granules with diameters of about 150-200 nm. We have recently reported on predominant electronic transport in printed films of Sepia formulated inks including the (insulating) binder Polyvinyl-butyral (PVB). In that work, we proposed that inter-granular percolative transport, observed for micrometric interelectrode distances, is promoted by the confining action of the PVB binder on the Sepia granules. Considering that inter-granular transport implies intra-granular transport, in this work we proceeded to a nanoscale study of Sepia granules by High Resolution Atomic Force Microscopy (HR-AFM) and Conductive-AFM (c-AFM). We have observed protrusions on the surface of the Sepia granules, suggesting sub-granular structures compatible with the hierarchical development of Sepia, as proposed elsewhere. For films of Sepia formulated inks deposited on gold-coated substrates, c-AFM revealed, for the very first time, a nanoscale electrical response. Nanoscale studies provide the key to structure-property relationships in biosourced materials strategic for sustainable organic electronics.

Electronic properties of lithium-ion battery cathodes studied in ion-gated transistor configuration.

Electronic and ionic transport governs lithium-ion battery (LIB) operation. The in operando study of electronic transport in lithium-ion transition metal oxide (LMOx) cathodes at different states of charge enables the evaluation of the state of health of LIBs and the optimization of their performance. We report on electronic transport in LIB cathode materials at different states of charge controlled in operando in ion-gated transistor (IGT) configuration. We considered LiNi0.5Mn0.3Co0.2O2 (NMC532)- and LiMn1.5Ni0.5O4 (LNMO)-based composite materials formulated like in conventional LIB cathodes and operated in the organic electrolyte LP30 (1M LiPF6 in ethylene carbonate:dimethyl carbonate 1:1 v/v). NMC532- and LNMO-based cathode materials were used as the transistor channel materials and LP30 as the ion gating medium. Beyond its impact on the field of LIBs, our work advances the design of novel devices based on mixed ionic and electronic transport, including neuromorphic computing.

Recovery of gold from e-waste via food waste byproducts.

Global materials' and energy constraints and environmental issues call for a holistic approach to waste upcycling. We propose a chemically rational, cost-effective and environmentally friendly recovery of non-leaching gold from e-waste using aqueous chemistry with hydrogen peroxide, an environmentally benign oxidant, and lactic acid, a food chain byproduct. The oxidation of the base metals enables the release of gold in its metallic state in the form of flakes subsequently separated via filtration. Our main byproduct is a precursor of Cu2O, a relevant metal oxide for solar energy conversion applications. The recovered gold was characterized by scanning electron microscopy, energy dispersive spectroscopy and x-ray photoelectron spectroscopy to gain insight into the morphology of the flakes and their chemical composition. Furthermore, recovered gold was used to successfully fabricate the source and drain electrodes in organic field-effect transistors.

High conductivity Sepia melanin ink films for environmentally benign printed electronics.

Melanins (from the Greek µÎ­λας, mélas, black) are bio-pigments ubiquitous in flora and fauna. Eumelanin is an insoluble brown-black type of melanin, found in vertebrates and invertebrates alike, among which Sepia (cuttlefish) is noteworthy. Sepia melanin is a type of bio-sourced eumelanin that can readily be extracted from the ink sac of cuttlefish. Eumelanin features broadband optical absorption, metal-binding affinity and antioxidative and radical-scavenging properties. It is a prototype of benign material for sustainable organic electronics technologies. Here, we report on an electronic conductivity as high as 10-3 S cm-1 in flexographically printed Sepia melanin films; such values for the conductivity are typical for well-established high-performance organic electronic polymers but quite uncommon for bio-sourced organic materials. Our studies show the potential of bio-sourced materials for emerging electronic technologies with low human- and eco-toxicity.

Biosourced quinones for high-performance environmentally benign electrochemical capacitors via interface engineering.

Biosourced and biodegradable organic electrode materials respond to the need for sustainable storage of renewable energy. Here, we report on electrochemical capacitors based on electrodes made up of quinones, such as Sepia melanin and catechin/tannic acid (Ctn/TA), solution-deposited on carbon paper engineered to create high-performance interfaces. Sepia melanin and Ctn/TA on TCP electrodes exhibit a capacitance as high as 1355 mF cm-2 (452 F g-1) and 898 mF cm-2 (300 F g-1), respectively. Sepia melanin and Ctn/TA symmetric electrochemical capacitors operating in aqueous electrolytes exhibit up to 100% capacitance retention and 100% coulombic efficiency over 50,000 and 10,000 cycles at 150 mA cm-2 (10 A g-1), respectively. Maximum power densities as high as 1274 mW cm-2 (46 kW kg-1) and 727 mW cm-2 (26 kW kg-1) with maximum energy densities of 0.56 mWh cm-2 (20 Wh kg-1) and 0.65 mWh cm-2 (23 Wh kg-1) are obtained for Sepia melanin and Ctn/TA.

Biodegradation of bio-sourced and synthetic organic electronic materials towards green organic electronics.

Ubiquitous use of electronic devices has led to an unprecedented increase in related waste as well as the worldwide depletion of reserves of key chemical elements required in their manufacturing. The use of biodegradable and abundant organic (carbon-based) electronic materials can contribute to alleviate the environmental impact of the electronic industry. The pigment eumelanin is a bio-sourced candidate for environmentally benign (green) organic electronics. The biodegradation of eumelanin extracted from cuttlefish ink is studied both at 25 °C (mesophilic conditions) and 58 °C (thermophilic conditions) following ASTM D5338 and comparatively evaluated with the biodegradation of two synthetic organic electronic materials, namely copper (II) phthalocyanine (Cu-Pc) and polyphenylene sulfide (PPS). Eumelanin biodegradation reaches 4.1% (25 °C) in 97 days and 37% (58 °C) in 98 days, and residual material is found to be without phytotoxic effects. The two synthetic materials, Cu-Pc and PPS, do not biodegrade; Cu-Pc brings about the inhibition of microbial respiration in the compost. PPS appears to be potentially phytotoxic. Finally, some considerations regarding the biodegradation test as well as the disambiguation of "biodegradability" and "bioresorbability" are highlighted.

Structure of the Electrical Double Layer at the Interface between an Ionic Liquid and Tungsten Oxide in Ion-Gated Transistors.

The structure of electrical double layers at electrified interfaces is of utmost importance for electrochemical energy storage as well as printable, flexible, and bioelectronic devices, such as ion-gated transistors (IGTs). Here we report a study based on atomic force microscopy force-distance profiling on electrical double layers forming at the interface between the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide and sol-gel films of mesoporous tungsten oxide. We successfully followed, under in operando conditions, the evolution of the arrangement of the ions at the interface with the tungsten oxide films used as channel materials in IGTs. Our work sheds light on the mechanism of operation of IGTs, thus offering the possibility of optimizing their performance.

Electronic Transport in the Biopigment Sepia Melanin.

Eumelanin is the most common form of the pigment melanin in the human body, with diverse functions including photoprotection, antioxidant behavior, metal chelation, and free radical scavenging. Melanin also plays a role in melanoma skin cancer and Parkinson's disease. Sepia melanin is a natural eumelanin extracted from the ink sac of cuttlefish. Eumelanin is an ideal candidate to eco-design technologies based on abundant, biosourced, and biodegradable organic electronic materials to alleviate the environmental footprint of the electronics sector. Herein, the focus is on the reversible electrical resistive switching in dry and wet Sepia eumelanin pellets, pointing to the possibility of predominant electronic transport satisfying conditio sine qua non to develop melanin-based electronic devices. These findings shed light on the possibility to describe the transport physics of dry eumelanin using the amorphous semiconductor model. Results are of tremendous importance for the development of sustainable organic electronics.

On the antioxidant activity of eumelanin biopigments: a quantitative comparison between free radical scavenging and redox properties.

The antioxidant activity of eumelanin, a ubiquitous pigment in flora and fauna, constitutes one of its most fascinating physicochemical properties. To shed light on free radical scavenging vs redox facets of such activity, we applied hydrogen atom transfer- and electron transfer-based assays to pristine Sepia ink, eumelanin from Sepia ink, chemically controlled eumelanins and their precursor building blocks. Our work contributes to the rational use of the antioxidant properties of eumelanin for health, cosmetics and environmental applications.

An Electrochemical Study on the Effect of Metal Chelation and Reactive Oxygen Species on a Synthetic Neuromelanin Model.

Neuromelanin is present in the cathecolaminergic neuron cells of the substantia nigra and locus coeruleus of the midbrain of primates. Neuromelanin plays a role in Parkinson's disease (PD). Literature reports that neuromelanin features, among others, antioxidant properties by metal ion chelation and free radical scavenging. The pigment has been reported to have prooxidant properties too, in certain experimental conditions. We propose an explorative electrochemical study of the effect of the presence of metal ions and reactive oxygen species (ROS) on the cyclic voltammograms of a synthetic model of neuromelanin. Our work improves the current understanding on experimental conditions where neuromelanin plays an antioxidant or prooxidant behavior, thus possibly contributing to shed light on factors promoting the appearance of PD.

Melanin: A Greener Route To Enhance Energy Storage under Solar Light.

The development of technologies integrating solar energy conversion and energy storage functions is critical for limiting the anthropogenic effects on climate change and preventing possible energy shortages related to the increase of the world population. In our work, we explored the possibility to integrate the conversion and storage functions within the same multifunctional biosourced material. We identified the redox-active, quinone-based, melanin pigment, featuring a broadband absorption in the UV-vis region, as the ideal candidate for such an exploration. Electrodes of melanin on carbon paper were investigated for their morphological, optical, and voltammetric characteristics prior to being assembled into symmetric supercapacitors operating in aqueous electrolytes. We observed that, under solar light, the capacity and capacitance of melanin electrodes significantly increase with respect to the dark conditions (by 22 and 39%, respectively). Once in a supercapacitor configuration, besides featuring a Coulombic efficiency close to 100% after 5000 cycles, the capacitance and capacity of the electrodes, rated by the initial values, improve after prolonged illumination, as it is the case for the energy and power density.

Electrolyte-gated transistors based on phenyl-C61-butyric acid methyl ester (PCBM) films: bridging redox properties, charge carrier transport and device performance.

The n-type organic semiconductor phenyl-C61-butyric acid methyl ester (PCBM), a soluble fullerene derivative well investigated for organic solar cells and transistors, can undergo several successive reversible, diffusion-controlled, one-electron reduction processes. We exploited such processes to shed light on the correlation between electron transfer properties, ionic and electronic transport as well as device performance in ionic liquid (IL)-gated transistors. Two ILs were considered, based on bis(trifluoromethylsulfonyl)imide [TFSI] as the anion and 1-ethyl-3-methylimidazolium [EMIM] or 1-butyl-1-methylpyrrolidinium [PYR14] as the cation. The aromatic structure of [EMIM] and its lower steric hindrance with respect to [PYR14] favor a 3D (bulk) electrochemical doping. As opposed to this, for [PYR14] the doping seems to be 2D (surface-confined). If the n-doping of the PCBM is pursued beyond the first electrochemical process, the transistor current vs. gate-source voltage plots in [PYR14][TFSI] feature a maximum that points to the presence of finite windows of high conductivity in IL-gated PCBM transistors.

Tin Dioxide Electrolyte-Gated Transistors Working in Depletion and Enhancement Modes.

Metal oxide semiconductors are interesting for next-generation flexible and transparent electronics because of their performance and reliability. Tin dioxide (SnO2) is a very promising material that has already found applications in sensing, photovoltaics, optoelectronics, and batteries. In this work, we report on electrolyte-gated, solution-processed polycrystalline SnO2 transistors on both rigid and flexible substrates. For the transistor channel, we used both unpatterned and patterned SnO2 films. Since decreasing the SnO2 area in contact with the electrolyte increases the charge-carrier density, patterned transistors operate in the depletion mode, whereas unpatterned ones operate in the enhancement mode. We also fabricated flexible SnO2 transistors that operate in the enhancement mode that can withstand moderate mechanical bending.

Photolithographically Patterned TiO2 Films for Electrolyte-Gated Transistors.

Metal oxides constitute a class of materials whose properties cover the entire range from insulators to semiconductors to metals. Most metal oxides are abundant and accessible at moderate cost. Metal oxides are widely investigated as channel materials in transistors, including electrolyte-gated transistors, where the charge carrier density can be modulated by orders of magnitude upon application of relatively low electrical bias (2 V). Electrolyte gating offers the opportunity to envisage new applications in flexible and printed electronics as well as to improve our current understanding of fundamental processes in electronic materials, e.g. insulator/metal transitions. In this work, we employ photolithographically patterned TiO2 films as channels for electrolyte-gated transistors. TiO2 stands out for its biocompatibility and wide use in sensing, electrochromics, photovoltaics and photocatalysis. We fabricated TiO2 electrolyte-gated transistors using an original unconventional parylene-based patterning technique. By using a combination of electrochemical and charge carrier transport measurements we demonstrated that patterning improves the performance of electrolyte-gated TiO2 transistors with respect to their unpatterned counterparts. Patterned electrolyte-gated (EG) TiO2 transistors show threshold voltages of about 0.9 V, ON/OFF ratios as high as 1 × 10(5), and electron mobility above 1 cm(2)/(V s).

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.

Self-assembly of indole-2-carboxylic acid at graphite and gold surfaces.

Model systems are critical to our understanding of self-assembly processes. As such, we have studied the surface self-assembly of a small and simple molecule, indole-2-carboxylic acid (I2CA). We combine density functional theory gas-phase (DFT) calculations with scanning tunneling microscopy to reveal details of I2CA assembly in two different solvents at the solution/solid interface, and on Au(111) in ultrahigh vacuum (UHV). In UHV and at the trichlorobenzene/highly oriented pyrolytic graphite (HOPG) interface, I2CA forms epitaxial lamellar structures based on cyclic OH⋯O carboxylic dimers. The structure formed at the heptanoic acid/HOPG interface is different and can be interpreted in a model where heptanoic acid molecules co-adsorb on the substrate with the I2CA, forming a bicomponent commensurate unit cell. DFT calculations of dimer energetics elucidate the basic building blocks of these structures, whereas calculations of periodic two-dimensional assemblies reveal the epitaxial effects introduced by the different substrates.

Conducting polymer transistors making use of activated carbon gate electrodes.

The characteristics of the gate electrode have significant effects on the behavior of organic electrochemical transistors (OECTs), which are intensively investigated for applications in the booming field of organic bioelectronics. In this work, high specific surface area activated carbon (AC) was used as gate electrode material in OECTs based on the conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) doped with poly(styrenesulfonate) (PSS). We found that the high specific capacitance of the AC gate electrodes leads to high drain-source current modulation in OECTs, while their intrinsic quasi-reference characteristics make unnecessary the presence of an additional reference electrode to monitor the OECT channel potential.

Titanyl phthalocyanine ambipolar thin film transistors making use of carbon nanotube electrodes.

The capability of efficiently injecting charge carriers into organic films and finely tuning their morphology and structure is crucial to improve the performance of organic thin film transistors (OTFTs). In this work, we investigate OTFTs employing carbon nanotubes (CNTs) as the source-drain electrodes and, as the organic semiconductor, thin films of titanyl phthalocyanine (TiOPc) grown by supersonic molecular beam deposition (SuMBD). While CNT electrodes have shown an unprecedented ability to improve charge injection in OTFTs, SuMBD is an effective technique to tune film morphology and structure. Varying the substrate temperature during deposition, we were able to grow both amorphous (low substrate temperature) and polycrystalline (high substrate temperature) films of TiOPc. Regardless of the film morphology and structure, CNT electrodes led to superior charge injection and transport performance with respect to benchmark Au electrodes. Vacuum annealing of polycrystalline TiOPc films with CNT electrodes yielded ambipolar OTFTs.

Carbon nanotube electrodes in organic transistors.

The scope of this Minireview is to provide an overview of the recent progress on carbon nanotube electrodes applied to organic thin film transistors. After an introduction on the general aspects of the charge injection processes at various electrode-semiconductor interfaces, we discuss the great potential of carbon nanotube electrodes for organic thin film transistors and the recent achievements in the field.

Eumelanin thin films: solution-processing, growth, and charge transport properties.

Eumelanin pigments show hydration-dependent conductivity, broad-band UV-vis absorption, and chelation of metal ions. Solution-processing of synthetic eumelanins opens new possibilities for the characterization of eumelanin in thin film form and its integration into bioelectronic devices. We investigate the effect of different synthesis routes and processing solvents on the growth, the morphology, and the chemical composition of eumelanin thin films using atomic force microscopy and X-ray photoelectron spectroscopy. We further characterize the films by transient electrical current measurements obtained at 50% to 90% relative humidity, relevant for bioelectronic applications. We show that the use of dimethyl sulfoxide is preferable over ammonia solution as processing solvent, yielding homogeneous films with surface roughnesses below 0.5 nm and a chemical composition in agreement with the eumelanin molecular structure. These eumelanin films grow in a quasi layer-by-layer mode, each layer being composed of nanoaggregates, 1-2 nm high, 10-30 nm large. The transient electrical measurements using a planar two-electrode device suggest that there are two contributions to the current, electronic and ionic, the latter being increasingly dominant at higher hydration, and point to the importance of time-dependent electrical characterization of eumelanin films.