Enhancing zT in Organic Thermoelectric Materials through Nanoscale Local Control Crystallization.

Organic thermoelectric materials are promising for wearable heating and cooling devices, as well as near-room-temperature energy generation, due to their nontoxicity, abundance, low cost, and flexibility. However, their primary challenge preventing widespread use is their reduced figure of merit (zT) caused by low electrical conductivity. This study presents a method to enhance the thermoelectric performance of solution-processable organic materials through confined crystallization using the lithographically controlled wetting (LCW) technique.

Tuning Electronic and Functional Properties in Defected MoS Films by Surface Patterning of Sulphur Atomic Vacancies.

Defects are inherent in transition metal dichalcogenides and significantly affect their chemical and physical properties. In this study, surface defect electrochemical nanopatterning is proposed as a promising method to tune in a controlled manner the electronic and functional properties of defective MoS₂ thin films. Using parallel electrochemical nanolithography, MoS₂ thin films are patterned, creating sulphur vacancy-rich active zones alternated with defect-free regions over a centimetre scale area, with sub-micrometre spatial resolution.

Morphology and Mechanics of Star Copolymer Ultrathin Films Probed by Atomic Force Microscopy in the Air and in Liquid.

Star copolymer films were produced by using spin-coating, drop-casting, and casting deposition techniques, thus obtaining ultrathin and thick films, respectively. The morphology is generally flat, but it becomes substrate-dependent for ultrathin films where the planarization effect of films is not efficient. The indentation hardness of films was investigated by Force Volume Maps in both the air and liquid.

Mesoscopic 3D Charge Transport in Solution-Processed Graphene-Based Thin Films: A Multiscale Analysis.

Graphene and related 2D material (GRM) thin films consist of 3D assembly of billions of 2D nanosheets randomly distributed and interacting via van der Waals forces. Their complexity and the multiscale nature yield a wide variety of electrical characteristics ranging from doped semiconductor to glassy metals depending on the crystalline quality of the nanosheets, their specific structural organization ant the operating temperature. Here, the charge transport (CT) mechanisms are studied that are occurring in GRM thin films near the metal-insulator transition (MIT) highlighting the role of defect density and local arrangement of the nanosheets.

Polymorph Separation by Ordered Patterning.

We herein address the problem of polymorph selection by introducing a general and straightforward concept based on their ordering. We demonstrated the concept by the ordered patterning of four compounds capable of forming different polymorphs when deposited on technologically relevant surfaces. Our approach exploits the fact that, when the growth of a crystalline material is confined within sufficiently small cavities, only one of the possible polymorphs is generated.

Indium-modified copper nanocubes for syngas production by aqueous CO electroreduction.

Electroreduction of carbon dioxide represents an appealing strategy to rethink a waste product as a valuable feedstock for the formation of value-added compounds. Among the metal electrodes able to catalyze such processes, copper plays a central role due to its rich chemistry. Strategies aimed at tuning Cu selectivity comprise nanostructuring and alloying/post-functionalization with heterometals.

All-Electrochemical Nanofabrication of Stacked Ternary Metal Sulfide/Graphene Electrodes for High-Performance Alkaline Batteries.

Energy-storage materials can be assembled directly on the electrodes of a battery using electrochemical methods, this allowing sequential deposition, high structural control, and low cost. Here, a two-step approach combining electrophoretic deposition (EPD) and cathodic electrodeposition (CED) is demonstrated to fabricate multilayer hierarchical electrodes of reduced graphene oxide (rGO) and mixed transition metal sulfides (NiCoMnS ). The process is performed directly on conductive electrodes applying a small electric bias to electro-deposit rGO and NiCoMnS in alternated cycles, yielding an ideal porous network and a continuous path for transport of ions and electrons.

Analysis of External and Internal Disorder to Understand Band-Like Transport in n-Type Organic Semiconductors.

Charge transport in organic semiconductors is notoriously extremely sensitive to the presence of disorder, both internal and external (i.e., related to interactions with the dielectric layer), especially for n-type materials.

Long-range selective transport of anions and cations in graphene oxide membranes, causing selective crystallization on the macroscale.

Monoatomic nanosheets can form 2-dimensional channels with tunable chemical properties, for ion storage and filtering applications. Here, we demonstrate transport of K, Na, and Li cations and F and Cl anions on the centimeter scale in graphene oxide membranes (GOMs), triggered by an electric bias. Besides ion transport, the GOM channels foster also the aggregation of the selected ions in salt crystals, whose composition is not the same as that of the pristine salt present in solution, highlighting the difference between the chemical environment in the 2D channels and in bulk solutions.

Ultrafast and Highly Sensitive Chemically Functionalized Graphene Oxide-Based Humidity Sensors: Harnessing Device Performances via the Supramolecular Approach.

Humidity sensors have been gaining increasing attention because of their relevance for well-being. To meet the ever-growing demand for new cost-efficient materials with superior performances, graphene oxide (GO)-based relative humidity sensors have emerged recently as low-cost and highly sensitive devices. However, current GO-based sensors suffer from important drawbacks including slow response and recovery, as well as poor stability.

Control of polymorphism in thiophene derivatives by sublimation-aided nanostructuring.

Here we applied a novel concept of "sublimation-aided nanostructuring" to control the polymorphism of a model material. The process exploits fractional precipitation as a tool for crystallisation in confinement using a templating agent that sublimes away from the system at the end of the process.

Enhanced control of self-doping in halide perovskites for improved thermoelectric performance.

Metal halide perovskites have emerged as promising photovoltaic materials, but, despite ultralow thermal conductivity, progress on developing them for thermoelectrics has been limited. Here, we report the thermoelectric properties of all-inorganic tin based perovskites with enhanced air stability. Fine tuning the thermoelectric properties of the films is achieved by self-doping through the oxidation of tin (ΙΙ) to tin (ΙV) in a thin surface-layer that transfers charge to the bulk.

3D to 2D reorganization of silver-thiol nanostructures, triggered by solvent vapor annealing.

Metal-organic composites are of great interest for a wide range of applications. The control of their structure remains a challenge, one of the problems being a complex interplay of covalent and supramolecular interactions. This paper describes the self-assembly, thermal stability and phase transitions of ordered structures of silver atoms and thiol molecules spanning from the molecular to the mesoscopic scale.

Highly Ordered Organic Ferroelectric DIPAB-Patterned Thin Films.

Ferroelectric molecular compounds present great advantages for application in electronics because they combine high polarization values, comparable to those of inorganic materials, with the flexibility and low-cost properties of organic ones. However, some limitations to their applicability are related to the high crystallinity required to deploy ferroelectricity. In this article, highly ordered ferroelectric patterned thin films of diisopropylammonium bromide have been successfully fabricated by a lithographically controlled wetting technique.

Reversible, Fast, and Wide-Range Oxygen Sensor Based on Nanostructured Organometal Halide Perovskite.

Nanostructured materials characterized by high surface-volume ratio hold the promise to constitute the active materials for next-generation sensors. Solution-processed hybrid organohalide perovskites, which have been extensively used in the last few years for optoelectronic applications, are characterized by a self-assembled nanostructured morphology, which makes them an ideal candidate for gas sensing. Hitherto, detailed studies of the dependence of their electrical characteristics on the environmental atmosphere have not been performed, and even the effect of a ubiquitous gas such as O has been widely overlooked.

Long-Lived Photoinduced Polarons in Organohalide Perovskites.

The long diffusion length of charge carriers in the CHNHPbI perovskite is one of the most relevant properties for explaining the high photovoltaic efficiency of perovskite solar cells. As a possible mechanism for the large diffusion length of electrons and holes, several authors suggested a reduced coulomb attraction of the carriers due to the formation of polarons. Here we performed continuous wave far-infrared photoinduced absorption (PIA) experiments on CHNHPbI; spectral changes are associated with local deformation of the lattice around the photogenerated long-lived charges, a typical signature of photoinduced polarons.

High, Anisotropic, and Substrate-Independent Mobility in Polymer Field-Effect Transistors Based on Preassembled Semiconducting Nanofibrils.

Achieving nanoscale control over the crystalline structure and morphology of electroactive polymer films and the possibility to transfer them onto any solid substrate are important tasks for the fabrication of high-performance organic/polymeric field-effect transistors (FETs). In this work, we demonstrate that ultrathin active layers preassembled at the water/air interface can possess high, anisotropic, and substrate-independent mobility in polymer FETs. By exploiting a modified approach to the Langmuir-Schaeffer technique, we self-assemble conjugated polymers in fibrillar structures possessing controlled thickness, nanoscale structure, and morphology; these highly ordered nanofibrils can be transferred unaltered onto any arbitrary substrate.

Fast-Response Photonic Device Based on Organic-Crystal Heterojunctions Assembled into a Vertical-Yet-Open Asymmetric Architecture.

Crystalline dioctyl-3,4,9,10-perylenedicarboximide nanowires and 6,13-bis(triisopropylsilylethynyl) pentacene microplates are integrated into a vertical-yet-open asymmetrical heterojunction for the realization of a high-performance organic photovoltaic detector, which shows fast photoresponse, ultrahigh signal-to-noise ratio, and high sensitivity to weak light.

Optical Input/Electrical Output Memory Elements based on a Liquid Crystalline Azobenzene Polymer.

Responsive polymer materials can change their properties when subjected to external stimuli. In this work, thin films of thermotropic poly(metha)acrylate/azobenzene polymers are explored as active layer in light-programmable, electrically readable memories. The memory effect is based on the reversible modifications of the film morphology induced by the photoisomerization of azobenzene mesogenic groups.

Surface induces different crystal structures in a room temperature switchable spin crossover compound.

We investigated the influence of surfaces in the formation of different crystal structures of a spin crossover compound, namely [Fe(L)2] (LH: (2-(pyrazol-1-yl)-6-(1H-tetrazol-5-yl)pyridine), which is a neutral compound thermally switchable around room temperature. We observed that the surface induces the formation of two different crystal structures, which exhibit opposite spin transitions, i.e.

Amorphous Aggregation of Amyloid Beta 1-40 Peptide in Confined Space.

The amorphous aggregation of Aβ1-40 peptide is addressed by using micromolding in capillaries. Both the morphology and the size of the aggregates are modulated by changing the contact angle of the sub-micrometric channel walls. Upon decreasing the hydrophilicity of the channels, the aggregates change their morphology from small aligned drops to discontinuous lines, thereby keeping their amorphous structure.

Direct On-Surface Patterning of a Crystalline Laminar Covalent Organic Framework Synthesized at Room Temperature.

We report herein an efficient, fast, and simple synthesis of an imine-based covalent organic framework (COF) at room temperature (hereafter, RT-COF-1). RT-COF-1 shows a layered hexagonal structure exhibiting channels, is robust, and is porous to N2 and CO2 . The room-temperature synthesis has enabled us to fabricate and position low-cost micro- and submicropatterns of RT-COF-1 on several surfaces, including solid SiO2 substrates and flexible acetate paper, by using lithographically controlled wetting and conventional ink-jet printing.

Mechanical and optical properties of ultralarge flakes of a metal-organic framework with molecular thickness.

The isolation of 2D-materials is already a success for graphene, graphene oxide, boron nitride and a few clays or metal chalcogenides, however despite the fact that some of them show very interesting physical properties, they lack useful functionalities. Metal-Organic Frameworks (MOFs) are multifunctional materials showing a wide range of physical and chemical properties that can be structurally designed by suitable selection of their building-blocks. This strategy may allow the production of layers with a variety of useful electronic and molecular recognition functionalities.

A multifunctional polymer-graphene thin-film transistor with tunable transport regimes.

Here we describe a strategy to fabricate multifunctional graphene-polymer hybrid thin-film transistors (PG-TFT) whose transport properties are tunable by varying the deposition conditions of liquid-phase exfoliated graphene (LPE-G) dispersions onto a dielectric surface and via thermal annealing post-treatments. In particular, the ionization energy (IE) of the LPE-G drop-cast on SiO2 can be finely adjusted prior to polymer deposition via thermal annealing in air environment, exhibiting values gradually changing from 4.8 eV up to 5.