Atomistic Simulations of P(NDI2OD-T2) Morphologies: From Single Chain to Condensed Phases

We investigate theoretically the structure, crystallinity, and solubility of a high-mobility n-type semiconducting copolymer, P(NDI2OD-T2), and we propose a set of new force field parameters. The force field is reparametrized against density functional theory (DFT) calculations, with the aim to reproduce the correct torsional angles that govern the polymer chain flexibility and morphology. We simulate P(NDI2OD-T2) oligomers in different environments, namely, in vacuo, in the bulk phase, and in liquid toluene and chloronaphthalene solution. The choice of these solvents is motivated by the fact that they induce different kinds of molecular preaggregates during the casting procedures, resulting in variable device performances. Our results are in good agreement with the available experimental data; the polymer bulk structure, in which the chains are quite planar, is correcly reproduced, yet the isolated chains are flexible enough to fold in vacuo. We also calculate the solubility of P(NDI2OD-T2) in toluene and chloronaphthalene, predicting a much better solubility of the polymer in the latter, also in accordance to experimental observations. Different morphologies and dynamics of the oligomers in the two solvents have been observed. The proposed parameters make it possible to obtain the description of P(NDI2OD-T2) in different environments and can serve as a basis for extensive studies of this polymer semiconductor, such as, for example, the dynamics of aggregation in solvent

U–Pb zircon geochronology of volcanic deposits from the Permian basin of the Orobic Alps (Southern Alps, Lombardy): chronostratigraphic and geological implications

U\u2013Pb zircon ages from volcanic rocks of Early Permian age (Southern Alps, Lombardy), associated with fault-controlled transtensional continental basins, were determined with the laser ablation (LA)-ICP-MS technique. Four samples were collected at the base and at the top of the up to 1000 m thick volcaniclastic unit of the Cabianca Volcanite. This unit pre-dates the development of a sedimentary succession that still contains, at different stratigraphic levels, volcanic intercalations. Age results from a tuff in the basal part of the unit constrain the onset of the volcanic activity to 280 \ub1 2.5 Ma. Ignimbritic samples from the upper part of the unit show a large scatter in the age distribution. This is interpreted as the occurrence of antecrystic and autocrystic zircons. The youngest autocrystic zircons (c. 270 Ma) are thus interpreted as better constraining the eruption age, constraining the duration of the volcanic activity in the Orobic Basin to about 10 Ma. The new geochronological results compared with those of other Early Permian basins of the Southern Alps reveal important differences that may reflect (1) a real time-transgressive beginning and end of the volcanic activity or (2) the complex mixing of antecrystic and autocrystic zircon populations in the analysed samples

Mapping Orientational Order of Charge-Probed Domains in a Semiconducting Polymer

Structure–property relationships are of fundamental importance to develop quantitative models describing charge transport in organic semiconductor based electronic devices, which are among the best candidates for future portable and lightweight electronic applications. While microstructural investigations, such as those based on X-rays, electron microscopy, or polarized optical probes, provide necessary information for the rationalization of transport in macromolecular solids, a general model predicting how charge accommodates within structural maps is not yet available. Therefore, techniques capable of directly monitoring how charge is distributed when injected into a polymer film and how it correlates to structural domains can help fill this gap. Supported by density functional theory calculations, here we show that polarized charge modulation microscopy (p-CMM) can unambiguously and selectively map the orientational order of the only conjugated segments that are probed by mobile charge in the few nanometer thick accumulation layer of a high-mobility polymer-based field-effect transistor . Depending on the specific solvent-induced microstructure within the accumulation layer, we show that p-CMM can image charge-probed domains that extend from submicrometer to tens of micrometers size, with markedly different degrees of alignment. Wider and more ordered p-CMM domains are associated with improved carrier mobility, as extracted from device characteristics. This observation evidences the unprecedented opportunity to correlate, directly in a working device, electronic properties with structural information on those conjugated segments involved in charge transport at the buried semiconductor–dielectric interface of a field-effect device

Complementary Organic Logic Gates on Plastic Formed by Self-Aligned Transistors with Gravure and Inkjet Printed Dielectric and Semiconductors

Complementary organic field-effect transistors, inverters, NAND and NOR logic on plastic are demonstrated using a combination of nanoimprint lithography, self-alignment, gravure, and inkjet printing. Sub-micrometer channel lengths, electrode overlaps and sub-100 nm dielectrics are compared to photolithographically patterned equivalents, as are inkjet and gravure printed semiconductors

Biodegradable All-Polymer Field-Effect Transistors Printed on Mater-Bi

The growing demand of disposable electronics raises serious concerns for the corresponding increase in the amount of electronic waste, with severe environmental impact. Organic and flexible electronics have been proposed long ago as a more sustainable and energy-efficient technological platform with respect to established ones. Yet, such technology is leading to a drastic increase of plastic waste if common approaches for flexible substrates are followed. In this scenario, biodegradable solutions can significantly limit the environmental impact, actively contributing to eliminate the waste streams (plastic or electronic) associated with disposal of devices. However, achieving suitably scalable processes to pattern mechanically robust organic electronics onto largely available biodegradable substrates is still an open challenge. In this work, all-organic and highly flexible field-effect transistors, inkjet printed onto the biodegradable and compostable commercial substrate Mater-Bi, are demonstrated. Because of the thermal instability of Mater-Bi, no annealing steps are applied, producing devices with limited carrier mobility, yet showing correct n-type behavior and robustness to bending and crumpling. The degradation behavior of the final system shows unaltered biodegradability level according to ISO 14851. These results represent a promising step toward sustainable flexible and large-area electronics, combining energy and materials efficient processes with largely available biodegradable substrates

A Rapidly Stabilizing Water-Gated Field-Effect Transistor Based on Printed Single-Walled Carbon Nanotubes for Biosensing Applications

Biosensors are expected to revolutionize disease management through provision of low-cost diagnostic platforms for molecular and pathogenic detection with high sensitivity and short response time. In this context, there has been an ever-increasing interest in using electrolyte-gated field-effect transistors (EG-FETs) for biosensing applications owing to their expanding potential of being employed for label-free detection of a broad range of biomarkers with high selectivity and sensitivity while operating at sub-volt working potentials. Although organic semiconductors have been widely utilized as the channel in EGFETs, primarily due to their compatibility with cost-effective low-temperature solution-processing fabrication techniques, alternative carbon-based platforms have the potential to provide similar advantages with improved electronic performances. Here, we propose the use of inkjet-printed polymer-wrapped monochiral singlewalled carbon nanotubes (s-SWCNTs) for the channel of EG-FETs in an aqueous environment. In particular, we show that our EG-CNTFETs require only an hour of stabilization before producing a highly stable response suitable for biosensing, with a drastic time reduction with respect to the most exploited organic semiconductor for biosensors. As a proof-of-principle, we successfully employed our water-gated device to detect the well-known biotin-streptavidin binding event

Submicrometer-Channel Organic Transistors with MHz Operation Range on Flexible Substrates by a Low-Resolution Fabrication Technique

In this paper, the development of a simple and reproducible approach for the fabrication of n-type organic field-effect transistors with a 350 nm-long channel on flexible substrates is reported. The critical feature of the device, the channel length, is obtained using a self-alignment process that exploits the vertical step of a plasma-etched thin Parylene C layer, according to the so-called step-edge architecture. The fabricated devices can operate in continuous mode and show an average and maximum transition frequency of 2.5 MHz and 5.5 MHz, respectively. The possibility of easily obtaining high-performing, short channel organic transistors on flexible substrates, without the use of expensive and high-resolution techniques, represents an interesting step toward the miniaturization of flexible circuits in the field of large-area organic electronics