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Adapting electronics to perfectly conform to non-planar and rough surfaces, such as human skin, is a very challenging task which, if solved, could open up new applications in fields of high economic and scientific interest ranging from health to robotics, wearable electronics, human machine interface and Internet of Things. The key to success lies in defining a technology that can lead to the fabrication of ultra-thin devices while exploiting materials that are ultimately thin, with high mechanical flexibility and excellent electrical properties. Here, we report a hybrid approach for the definition of high-performance, ultra-thin and conformable electronic devices and circuits, based on the integration of ultimately thin semiconducting transition metal dichalcogenides (TMDC), i.e., MoS2, with organic gate dielectric material, i.e., polyvinyl formal (PVF) combined with the ink-jet printing of conductive PEDOT:PSS ink for electrodes definition. Through this cost-effective, fully bottom-up and solution-based approach, transistors and simple digital and analogue circuits are fabricated by a sequential stacking of ultrathin (nanometer) layers on a few micron thick polyimide substrate, which guarantees the high flexibility mandatory for the targeted applications.

Research on conjugated polymers for thermoelectric applications has made tremendous progress in recent years, which is accompanied by surging interest in molecular doping as a means to achieve the high electrical conductivities that are required. A detailed understanding of the complex relationship between the doping process, the structural as well as energetic properties of the polymer films, and the resulting thermoelectric behavior is slowly emerging. This review summarizes recent developments and strategies that permit enhancing the electrical conductivity of p- and n-type conjugated polymers via molecular doping. The impact of the chemical design of both the polymer and the dopant, the processing conditions, and the resulting nanostructure on the doping efficiency and stability of the doped state are discussed. Attention is paid to the interdependence of the electrical and thermal transport characteristics of semiconductor host-dopant systems and the Seebeck coefficient. Strategies that permit to improve the thermoelectric performance, such as an uniaxial alignment of the polymer backbone in both bulk and thin film geometries, manipulation of the dielectric constant of the polymer, and the variation of the dopant size, are explored. A combination of theory and experiment is predicted to yield new chemical design principles and processing schemes that will ultimately give rise to the next generation of organic thermoelectric materials.

There is growing interest in transitioning electronic components and circuitry from stiff and rigid substrates to more flexible and stretchable platforms, such as thin plastics, textiles, and foams. In parallel, the push for more sustainable, biocompatible, and cost-efficient conductive inks to coat these substrates, has led to the development of formulations with novel nanomaterials. Among these, 2D materials, and particularly graphenes and MXenes, have received intense research interest due to their increasingly facile and scalable production, high electrical conductivity, and compatibility with existing manufacturing techniques. They enable a range of electronic devices, including strain and pressure sensors, supercapacitors, thermoelectric generators, and heaters. These new flexible and stretchable electronic devices developed with 2D material coatings are poised to unlock exciting applications in the wearable, healthcare and Internet of Things sectors. This review has surveyed key data from more than 200 articles published over the last 6 years, to provide a quantitative analysis of recent progress in the field and shade light on future directions and prospects of this technology. We find that despite the different chemical origins of graphenes and MXenes, their shared electrical properties and 2D morphology, guarantee intriguing performance in end applications, leaving plenty of space for shared progress and advancements in the future.

Edible electronics will facilitate point-of-care testing through safe and cheap devices that are digested or degraded in the body or environment after performing a specific function. Its thrive depends on creating a library of materials that are the basic building blocks for eatable technologies. Edible electrical conductors fabricated with green methods that allow production at a large scale and composed of food derivatives, ingestible in large amounts without risk for human health are needed. Here, conductive pastes made with materials with a high tolerable upper intake limit (major of mg/kg body weight /day) are proposed. Conductive oleogel paste composites, made with biodegradable and food-grade materials like natural waxes, oils, and activated carbon conductive fillers, are presented. The proposed pastes are compatible with manufacturing processes such as direct ink writing and thus are suitable for an industrial scale-up. These conductors are built without the use of solvents, and with tunable electromechanical features and adhesion depending on the composition. They have antibacterial and hydrophobic properties, so that they can be used in contact with food preventing contamination and preserving its organoleptic properties. As a proof-of-principle application, the edible conductive pastes are demonstrated to be effective edible contacts for food impedance analysis, to be integrated for example in smart fruit labels for ripening monitoring.

Solution-processed, large-area, and flexible electronics largely relies on the excellent electronic properties of sp$^2$-hybridized carbon molecules, either in the form of $\pi$-conjugated small molecules and polymers or graphene and carbon nanotubes. Carbon with sp-hybridization, the foundation of the elusive allotrope carbyne, offers vast opportunities for functionalized molecules in the form of linear carbon atomic wires (CAWs), with intriguing and even superior predicted electronic properties. While CAWs represent a vibrant field of research, to date, they have only been applied sparingly to molecular devices. The recent observation of the field-effect in microcrystalline cumulenes suggests their potential applications in solution-processed thin-film transistors but concerns surrounding the stability and electronic performance have precluded developments in this direction. In the present study, ideal field-effect characteristics are demonstrated for solution-processed thin films of tetraphenyl[3]cumulene, the shortest semiconducting CAW. Films are deposited through a scalable, large-area, meniscus-coating technique, providing transistors with hole mobilities in excess of 0.1 cm$^2$ V$^{-1}$ s$^{-1}$, as well as promising operational stability under dark conditions. These results offer a solid foundation for the exploitation of a vast class of molecular semiconductors for organic electronics based on sp-hybridized carbon systems and create a previously unexplored paradigm.

Substrate engineering for steering cell growth is a wide and well-established area of research in the field of modern biotechnology. Here we introduce a micromachining technique to pattern an inert, transparent polymer matrix blended with a photoactive polymer. We demonstrate that the obtained scaffold combines the capability to align with that to photostimulate living cells. This technology can open up new and promising applications, especially where cell alignment is required to trigger specific biological functions, e.g. generate powerful and efficient muscle contractions following an external stimulus., Comment: 30 pages, 7 images in main text, 5 images in supporting

Organic printed electronics has proven its potential as an essential enabler for applications related to healthcare, entertainment, energy and distributed intelligent objects. The possibility of exploiting solution-based and direct-writing production schemes further boosts the benefits offered by such technology, facilitating the implementation of cheap, conformable, bio-compatible electronic applications. The result shown in this work challenges the widespread assumption that such class of electronic devices is relegated to low-frequency operation, owing to the limited charge mobility of the materials and to the low spatial resolution achievable with conventional printing techniques. Here, it is shown that solution-processed and direct-written organic field-effect transistors can be carefully designed and fabricated so to achieve a maximum transition frequency of 160 MHz, unlocking an operational range that was not available before for organics. Such range was believed to be only accessible with more performing classes of semiconductor materials and/or more expensive fabrication schemes. The present achievement opens a route for cost- and energy-efficient manufacturability of flexible and conformable electronics with wireless-communication capabilities.

2D quantum confined hybrid materials are of great interest from a solid state physics standpoint because of the rich multibody phenomena hosted, their tunability and easy synthesis allowing to create material libraries. In addition, from a technological standpoint, 2D hybrids are promising candidates for efficient, tunable, low cost materials impacting a broad range of optoelectronic devices. Different approaches and materials have therefore been investigated, with the notable example of 2D metal halide hybrid perovskites. Despite the remarkable properties of such materials, the presence of toxic elements like lead are not desirable in applications and their ionic lattices may represent a limiting factor for stability under operating conditions. Alternative, non-ionic 2D materials made of non-toxic elements are therefore desirable. In order to expand the library of possible hybrid quantum wells materials, here we consider an alternative platform based on non-toxic, self-assembled, metal-organic chalcogenides. While the optical properties have been recently explored and some unique excitonic characters highlighted, photo-generation of carriers and their transport in these lamellar inorganic/organic nanostructures, critical optoelectronic aspects, remain totally unexplored. We hereby report the first electrical investigation of the air-stable [AgSePh] 2D coordination polymer in form of nanocrystal (NC) films readily synthesized in situ and at low temperature, compatible with flexible plastic substrates. The wavelength-dependent photo-response of the NC films suggests possible use of this materials as near-UV photodetector. We therefore built a lateral photo-detector, achieving a sensitivity of 0.8 A/W at 370 nm thanks to a photoconduction mechanism, and a cutoff frequency of ~400 Hz, and validated its reliability as air-stable UV detector on flexible substrates.

Silver benzeneselenolate [AgSePh] is a coordination polymer that hosts a hybrid quantum well structure. The recent advancements in the study of its tightly bound excitons (~300 meV) and photoconductive properties (recently employed in UV photodetection) makes it an interesting representative of a material platform that is an environmentally stable alternative to 2D metal halide perovskites in terms of optoelectronic properties. To this aim, several challenges are to be addressed, among which the lack of control over the metal-organic reaction process in the reported synthesis of the [AgSePh] nanocrystal film (NC). This issue contributed to cast doubts over the origin of its intra-bandgap electronic states. In this article we study all the steps to obtain phase pure [AgSePh] NC films, from thin silver films through its oxidation and reaction via a chemical vapor-solid with benzeneselenol, by means of UV-vis, XRD, SEM, and AFM. Raman and FTIR spectroscopy are also employed to provide vibrational peaks assignment, for the first time on this polymer. Our analysis supports an acid-base reaction scheme based on an acid attacking the metal oxide precursor, generating water as byproduct of the polymeric synthesis, speeding up the reaction by solvating the PhSeH. The reaction readily goes to completion within 30 min in a supersaturated PhSeH / N2 atmosphere at 90 {\deg}C. Our analysis suggests the absence of precursor's leftovers or oxidized species that could contribute to the intra-gap states. By tuning the reaction parameters, we gained control on film morphology to obtain substrate-parallel oriented micro-crystals showing different excitonic absorption intensities. Finally, centimeters size high quality [AgSePh] NC films could be obtained, enabling exploitation of their optoelectronic properties, such as UV photodetection, in large-area applications.

Solution-processed networks of semiconducting, single-walled carbon nanotubes (SWCNTs) have attracted considerable attention as materials for next-generation electronic devices and circuits. However, the impact of the SWCNT network composition on charge transport on a microscopic level remains an open and complex question. Here, we use charge-modulated absorption and photoluminescence spectroscopy to probe exclusively the mobile charge carriers in monochiral (6,5) and mixed SWCNT network field-effect transistors. Ground state bleaching and charge-induced trion absorption features, as well as exciton quenching are observed depending on applied voltage and modulation frequency. Through correlation of the modulated mobile carrier density and the optical response of the nanotubes, we find that charge transport in mixed SWCNT networks depends strongly on the diameter and thus bandgap of the individual species. Mobile charges are preferentially transported by small bandgap SWCNTs especially at low gate voltages, whereas large bandgap species only start to participate at higher carrier concentrations. Our results demonstrate the excellent suitability of modulation spectroscopy to investigate charge transport in nanotube network transistors and highlight the importance of SWCNT network composition for their performance., Comment: ACS Nano 2020

Oligothiophenes are pi-conjugated semiconducting and fluorescent molecules whose self-assembly properties are widely investigated for application in organic electronics, optoelectronics, biophotonics and sensing. We report here an approach to the preparation of crystalline oli-gothiophene nano/micro-fibers based on the use of a sulfur overrich quaterthiophene building block, -T4S4-, containing in its covalent network all the information needed to promote the di-rectional, pi-pi stacking driven, self-assembly of Ar-T4S4-Ar oligomers into fibers with hierar-chical supramolecular arrangement from nano- to microscale. We show that when Ar varies from unsubstituted thiophene to thiophene substituted with electron withdrawing groups, a wide redistribution of the molecular electronic charge takes place without substantially affecting the aggregation modalities of the oligomer. In this way a structurally comparable series of fibers is obtained having progressively varying optical properties, redox potentials, photoconductivity and type of prevailing charge carriers (from p- to n-type). A thorough characterization of the fi-bers based on SEM, CD, CV, X-ray diffraction, UV-vis and PL spectroscopies, photoconductivi-ty and KPFM measurements is reported. With the aid of DFT calculations, combined with X-ray data, a model accounting for the growth of the fibers from molecular to nano- and microscale is proposed. We believe that the simple strategy outlined in this study allows to establish a straightforward correlation between the molecular structure of the components and the function-al properties of the corresponding self-assembled nano/micro-fibers.

Indacenodithiophene (IDT) based materials are emerging high performance conjugated polymers for use in efficient organic photovoltaics and transistors. However, their preparation generally suffers from long reaction sequences and is often accomplished using disadvantageous Stille couplings. Herein, we present detailed synthesis pathways to IDT homopolymers using C-H activation for all C-C coupling steps. Polyketones are first prepared by direct arylation polycondensation (DAP) in quantitative yield and further cyclized polymer analogously. This protocol is suitable for obtaining structurally well-defined IDT homopolymers, provided that the conditions for cyclization are chosen appropriately and that side reactions are suppressed. Moreover, this polymer analogous pathway gives rise to asymmetric side chain patterns, which allows to fine tune physical properties. Alternatively, IDT homopolymers can be obtained via oxidative direct arylation polycondensation of IDT monomers (oxDAP), leading to IDT homopolymers with similar properties but at reduced yield. Detailed characterization by NMR, IR, UV-vis and PL spectroscopy, and thermal properties, is used to guide synthesis and to explain varying field-effect transistor hole mobilities in the range of 10-6- 10-3 cm2/Vs.

It is still a matter of controversy whether the relative difference in hole and electron transport in solution-processed organic semiconductors is either due to intrinsic properties linked to chemical and solid-state structure or to extrinsic factors, as device architecture. We here isolate the intrinsic factors affecting either electron or hole transport within the same film microstructure of a model copolymer semiconductor. Relatively, holes predominantly bleach inter-chain interactions with H-type electronic coupling character, while electrons' relaxation more strongly involves intra-chain interactions with J-type character. Holes and electrons mobility correlates with the presence of a charge transfer state, while their ratio is a function of the relative content of intra- and inter-molecular interactions. Such fundamental observation, revealing the specific role of the ground-state intra- and inter-molecular coupling in selectively assisting charge transport, allows predicting a more favorable hole or electron transport already from screening the polymer film ground state optical properties.

Recent demonstrations of inverted thermal activation of charge mobility in polymer field-effect transistors have excited the interest in transport regimes not limited by thermal barriers. However, rationalization of the limiting factors to access such regimes is still lacking. An improved understanding in this area is critical for development of new materials, establishing processing guidelines, and broadening of the range of applications. Here we show that precise processing of a diketopyrrolopyrrole-tetrafluorobenzene-based electron transporting copolymer results in single crystal-like and voltage-independent mobility with vanishing activation energy above 280 K. Key factors are uniaxial molecular alignment and thermal annealing at temperatures within the melting endotherm of films. Experimental and computational evidence converge toward a picture of electrons being delocalized within crystalline domains of increased size. Residual energy barriers introduced by disordered regions are bypassed in the direction of molecular alignment by a more efficient interconnection of the ordered domains following the annealing process.

Organic thermoelectrics are attractive for the fabrication of flexible and cost-effective thermoelectric generators (TEGs) for waste heat recovery, in particular by exploiting large-area printing of polymer conductors. Efficient TEGs require both p- and n-type conductors: so far, the air instability of polymer n-type conductors, which typically loose orders of magnitude in electrical conductivity ({\sigma}) even for short exposure time to air, has impeded processing under ambient conditions. Here we tackle this problem in a relevant class of electron transporting, naphthalene-diimide co-polymers, by substituting the imide oxygen with sulphur. n-type doping of the thionated co-polymer gives rise to a higher {\sigma} with respect to the non-thionated one, and most importantly, owing to a reduced energy level of the lowest-unoccupied molecular orbital, {\sigma} is substantially stable over 16 h of air exposure. This result highlights the effectiveness of chemical tuning to improve air-stability of n-type solution-processable polymer conductors and shows a path towards ambient large-area manufacturing of efficient polymer TEGs.

Organic printed electronics is proving its suitability for the development of wearable, lightweight, distributed applications in combination with cost-effective production processes. Nonetheless, some necessary features for several envisioned disruptive mass-produced products are still lacking: among these radio-frequency (RF) communication capability, which requires high operational speed combined with low supply voltage in electronic devices processed on cheap plastic foils. Here, we demonstrate that high-frequency, low-voltage, polymer field-effect transistors can be fabricated on plastic with the sole use of a combination of scalable printing and digital laser-based techniques. These devices reach an operational frequency in excess of 1 MHz at the challengingly low bias voltage of 2 V, and exceed 14 MHz operation at 7 V. In addition, when integrated into a rectifying circuit, they can provide a DC voltage at an input frequency of 13.56 MHz, opening the way for the implementation of RF devices and tags with cost-effective production processes.

In the path toward the integration of organic field effect transistors (OFETs) and logic circuits into low-cost and mass produced consumer products, all-organic devices based on printed semiconductors are one of the best options to meet stringent costs requirements. Within this framework, it is still challenging to achieve low voltage operation, as required by the use of thin film batteries and energy harvesters, for which a high capacitance and reliable organic dielectric is required. Here, the development of a parylene-C based dielectric bilayer compatible with top-gate architectures for low-voltage OFETs and logic circuits is presented. The polymer bilayer dielectric allowed the high yield fabrication of all-polymer, bendable, transparent p- and n-type OFETs operating below 2 V, with low leakage, uniform performances and high yield. Such result is a key enabler for the reliable realization of complementary logic circuits that can operate already at a voltage bias of 2 V, such as well-balanced inverters, ring-oscillators and D-Flip-Flops.

Cell-based biosensors constitute a fundamental tool in biotechnology, and their relevance has greatly increased in recent years as a result of a surging demand for reduced animal testing and for high-throughput and cost-effective in vitro screening platforms dedicated to environmental and biomedical diagnostics, drug development and toxicology. In this context, electrochemical/electronic cell-based biosensors represent a promising class of devices that enable long-term and real-time monitoring of cell physiology in a non-invasive and label-free fashion, with a remarkable potential for process automation and parallelization. Common limitations of this class of devices at large include the need for substrate surface modification strategies to ensure cell adhesion and immobilization, limited compatibility with complementary optical cell-probing techniques, and need for frequency-dependent measurements, which rely on elaborated equivalent electrical circuit models for data analysis and interpretation. We hereby demonstrate the monitoring of cell adhesion and detachment through the time-dependent variations in the quasi-static characteristic current curves of a highly stable electrolyte-gated transistor, based on an optically transparent network of printable polymer-wrapped semiconducting carbon-nanotubes.

Thanks to recent progress in terms of materials properties, polymer field-effect transistors (FETs) operating in the MHz range can be achieved. However, further development towards challenging frequency ranges, for a field accustomed to slow electronic devices, has to be addressed with suitable device design and measurements methodologies. In this work, we report n-type FETs based on a solution-processed polymer semiconductor where the critical features have been realized by a large-area compatible direct-writing technique, allowing to obtain a maximum frequency of transition of 19 MHz, as measured by means of Scattering Parameters (S-Parameters). This is the first report of solution-processed organic FETs characterized with S-Parameters., Comment: 4 pages, 3 figures. IEEE Electron Device Letters (2019)

An optimized direct arylation polycondensation (DAP) protocol for the synthesis of a novel naphthalene diimide (NDI) 2,2'-bithiazole (2-BTz) copolymer (PNDI-2-BTz) is presented. The regioselective C-H activation of 2-BTz at the 5-positions allows for the synthesis of fully regioregular and homocoupling-free PNDI-2-BTz of high molecular weight in less than 1 h in quantitative yield. Complete end group assignment shows functionalities according to monomer structures or to nucleophilic substitution, and allows for the reliable determination of absolute molecular weight. Compared to the well-known bithiophene analog PNDIT2, an exceptionally high thermal stability, a hypsochromically shifted charge transfer absorption band and a lower-lying LUMO energy level is found, making PNDI-2-BTz an interesting candidate for applications in organic electronic devices. In contrast to the selective and high yielding C-H activation of 2-BTz at the 5-position, the regioisomer 5,5'-bithiazole is inactive under a variety of conditions.

Conformable Electronics refers to a class of electronic devices that have the ability to conformally adhere onto non-planar surfaces and materials, resulting particularly appealing for skin applications, such as the case of skin-worn unobtrusive (bio)sensors for healthcare monitoring. Conformability can be addressed by integrating basic electronic components on ultrathin polymeric film substrates. Among other basic electronic components, capacitors are fundamental ones for energy storage, sensing, frequency tuning, impedance adaptation and signal processing. In this work we present a novel approach for conformable capacitors based on a free-standing, ultrathin and ultra-conformable nanosheets of poly (vinyl formal) (PVF), which serve both as structural and dielectric component of the capacitor. A novel fabrication approach is proposed and applied to fully free-standing ultrathin capacitors fabrication, having an overall thickness as low as 200 nm; that represents, to the best of our knowledge, the thinnest free-standing capacitors ever reported. Thanks to the ultra-low thickness, the proposed capacitors are able to sustain flexure to extremely small curvature radii (as low as 1.5 {\mu}m) and to conform to complex surfaces, such as a nylon mesh with micrometric texture without compromising their operation.

The depth dependence of crystalline structure within thin films is critical for many technological applications, but has been impossible to measure directly using common techniques. In this work, by monitoring diffraction peak intensity and location and utilizing the highly angle-dependent waveguiding effects of X-rays near grazing incidence we quantitatively measure the thickness, roughness and orientation of stratified crystalline layers within thin films of a high-performance semiconducting polymer. In particular, this diffractive X-ray waveguiding reveals a self-organized 5-nm-thick crystalline surface layer with crystalline orientation orthogonal to the underlying 65-nm-thick layer. While demonstrated for an organic semiconductor film, this approach is applicable to any thin film material system where stratified crystalline structure and orientation can influence important interfacial processes such as charge injection and field-effect transport.

The use of natural or bioinspired materials to develop edible electronic devices is a potentially disruptive technology that can boost point-of-care testing. The technology exploits devices which can be safely ingested, along with pills or even food, and operated from within the gastrointestinal tract. Ingestible electronics could potentially target a significant number of biomedical applications, both as therapeutic and diagnostic tool, and this technology may also impact the food industry, by providing ingestible or food-compatible electronic tags that can smart track goods and monitor their quality along the distribution chain. We hereby propose temporary tattoo-paper as a simple and versatile platform for the integration of electronics onto food and pharmaceutical capsules. In particular, we demonstrate the fabrication of all-printed Organic Field-Effect Transistors (OFETs) on untreated commercial tattoo-paper, and their subsequent transfer and operation on edible substrates with a complex non-planar geometry.

Solution-processed organic semiconductors enable the fabrication of large-area and flexible electronics by means of cost-effective, solution-based mass manufacturing techniques. However, for many applications an insoluble active layer can offer technological advantages in terms of robustness to processing solvents. This is particularly relevant in field-effect transistors (FET), where processing of dielectrics or barriers from solution on top of the semiconductor layer typically imposes the use of orthogonal solvents in order not to interfere with the nanometer thick accumulation channel. To this end, the use of latent pigments, highly soluble molecules which can produce insoluble films after a post-deposition thermal cleavage of solubilizing groups, is a very promising strategy. In this contribution, we demonstrate the use of tert-Butyloxycarbonyl (t-Boc) functionalized diketopyrrolopyrrole and perylene-diimide small molecules for good hole and electron transporting films. t-Boc thermal cleavage produces a densification of the films, along with a strong structural rearrangement of the deprotected molecules, strongly improving charge mobility in both p- and n-type FET. We also highlight the robustness of these highly insoluble semiconducting layers to typical and aggressive processing solvents. These results can greatly enhance the degree of freedom in the manufacturing of multi-layered organic electronic devices, offering enhanced stability to harsh processing steps.

Printed polymer electronics has held for long the promise of revolutionizing technology by delivering distributed, flexible, lightweight and cost-effective applications for wearables, healthcare, diagnostic, automation and portable devices. While impressive progresses have been registered in terms of organic semiconductors mobility, field-effect transistors (FET), the basic building block of any circuit, are still showing limited speed of operation, thus limiting their real applicability. So far, attempts with organic FET to achieve the tens of MHz regime, a threshold for many applications comprising the driving of high resolution displays, have relied on the adoption of sophisticated lithographic techniques and/or complex architectures, undermining the whole concept. In this work we demonstrate polymer FETs which can operate up to 20 MHz and are fabricated by means only of scalable printing techniques and direct-writing methods with a completely mask-less procedure. This is achieved by combining a fs-laser process for the sintering of high resolution metal electrodes, thus easily achieving micron-scale channels with reduced parasitism down to 0.19 pF mm-1, and a large area coating technique of a high mobility polymer semiconductor, according to a simple and scalable process flow.