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. Herein we isolate 2D-MOF flakes with areas of hundreds of square microns and an excellent control of the molecular thickness (from single up to ca. 50 layers). The samples exhibit such good photoluminescence and mechanical properties as to allow free-standing characterization of few layers' flakesThe authors acknowledge financial support from MICINN (MAT2013-46753-C2-1-P and MAT2013-46753-C2-2-P and Consolider CSD2010-00024

Selective Electrodesorption-Based Atomic Layer Deposition (SEBALD) of Bismuth under Morphological Control

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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. We verify our method by utilizing several model compounds to fabricate micrometric "logic patterns" in which each of the printed pixels is easily identifiable as comprising only one polymorph and can be individually accessed for further operations

Control of polymorphism in thiophene derivatives by sublimation-aided nanostructuring

Here we applied the concept of "sublimation-aided nanostructuring" to control the polymorphism of a model material

Semicrystalline Polythiophene-Based Nanoparticles Deposited from Water on Flexible PET/ITO Substrates as a Sustainable Approach toward Long-Lasting Solid-State Electrochromic Devices

info:eu-repo/grantAgreement/EC/H2020/734834/EU FCT/MEC (UIDB/50006/2020). PhD grant SFRH/BD/139171/2018 from FCT/MCTES. We are very grateful to Dr. Carlos Pinheiro and Ynvisible company for discussions and assistance in the assembly of the electrochromic devices.We report the use of films of poly(3-hexylthiophene-2,5-diyl) nanoparticles (P3HT-NPs) prepared with the reprecipitation method employing water as solvent in the absence of surfactants for solid-state electrochromic devices (ECDs) and prove that these displays present enhanced properties when compared to similar ECDs with thin films deposited from chloroform. Films of differently sized nanoparticles (100 to 400 nm) were prepared and spray-coated on flexible PET-ITO substrates and tested for electrochromic properties. ECDs with switching times (t(90)) of 4 s were obtained using P3HT-NPs with a diameter of 100 nm, while those built using P3HT thin film presented longer switching speeds over 13 s for reduction (bleached to colored state). Additionally, the devices were subjected to 1000 cycles using -1.5 V/1.5 V, and the displays using P3HT 100 nm NPs presented higher transmittances (Delta(T) = +/- 20%) when compared with devices with P3HT thin film due to a more efficient oxidation step. Our data show that the availability of colloidal nanoparticles made of conjugated polymers deposited from water is an environmentally sustainable strategy leading to electrochromic devices with improved properties.authorsversionpublishe

Controlling Ambipolar Transport and Voltage Inversion in Solution-Processed Thin-Film Devices through Polymer Blending

Ambipolar semiconductors are attracting a great interest as building blocks for photovoltaics and logic applications. Field-effect transistors built on solution-processable ambipolar materials hold strong promise for the engineering of large-area low-cost logic circuits with a reduced number of devices components. Such devices still suffer from a number of obstacles including the challenging processing, the low Ion/Ioff, the unbalanced mobility, and the low gain in complementary metal–oxide–semiconductor (CMOS)-like circuits. Here, we demonstrate that the simple approach of blending commercially available n- and p-type polymers such as P(NDI2OD-T2), P3HT, PCD-TPT, PDVT-8, and IIDDT-C3 can yield high-performing ambipolar field-effect transistors with balanced mobilities and Ion/Ioff > 10^7. Each single component was studied separately and upon blending by means of electrical characterization, ambient ultraviolet photoelectron spectroscopy, atomic force microscopy, and grazing incidence wide angle X-ray scattering to unravel the correlation between the morphology/structure of the semiconducting films and their functions. Blends of n- and p-type semiconductors were used to fabricate CMOS-like inverter circuits with state-of-the-art gains over 160 in the case of P(NDI2OD-T2) blended with PDVT-8. Significantly, our blending approach was successful in producing semiconducting films with balanced mobilities for each of the four tested semiconductor blends, although the films displayed different structural and morphological features. Our strategy, which relies on establishing a correlation between ambipolar performances, film morphology, molecular structure, and blending ratio, is extremely efficient and versatile; thus it could be applied to a wide range of polymers or solution processable small molecules

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 (NiCoMnSx). The process is performed directly on conductive electrodes applying a small electric bias to electro-deposit rGO and NiCoMnSx in alternated cycles, yielding an ideal porous network and a continuous path for transport of ions and electrons. A fully rechargeable alkaline battery (RAB) assembled with such electrodes gives maximum energy density of 97.2 Wh kg−1 and maximum power density of 3.1 kW kg−1, calculated on the total mass of active materials, and outstanding cycling stability (retention 72% after 7000 charge/discharge cycles at 10 A g−1). When the total electrode mass of the cell is considered, the authors achieve an unprecedented gravimetric energy density of 68.5 Wh kg−1, sevenfold higher than that of typical commercial supercapacitors, higher than that of Ni/Cd or lead–acid Batteries and similar to Ni–MH Batteries. The approach can be used to assemble multilayer composite structures on arbitrary electrode shapes

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 struc-ture remains a challenge, one of the problems being a complex interplay of covalent and supramolecularinteractions. This paper describes the self-assembly, thermal stability and phase transitions of orderedstructures of silver atoms and thiol molecules spanning from the molecular to the mesoscopic scale.Building blocks of molecularly defined clusters formed from 44 silver atoms, each particle coated by amonolayer of 30 thiol ligands, are used as ideal building blocks. By changing solvent and temperature it ispossible to tune the self-assembled 3D crystals of pristine nanoparticles or, conversely, 2D layered structures, with alternated stacks of Ag atoms and thiol monolayers. The study investigates morphological,chemical and structural stability of these materials between 25 and 300 °Cin situandex situat the nano-scale by combining optical and electronic spectroscopic and scattering techniques, scanning probemicroscopies and density-functional theory (DFT) calculations. The proposed wet-chemistry approach isrelatively cheap, easy to implement, and scalable, allowing the fabricated materials with tuned propertiesusing the same building blocks

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

Multi-modal sensing in spin crossover compounds

We exploited the solvatochromic spin-state switching in a spin crossover (SCO) compound based on the Fe-II complex and the simultaneous change of spectroscopic properties for selective multimodal sensing of methanol and ethanol. We demonstrate that sensing capabilities are due to the inclusion of methanol or ethanol molecules into the crystalline structure, which tailors simultaneously the transition temperature, colour, birefringence and vibrational modes. We exploited this capability by integrating a neutral compound, switchable at room temperature, into a micrometric TAG sensitive to the colour and birefringence. The system was characterised by optical microscopy, magnetic susceptibility, Raman spectroscopy and X-ray diffraction