Low-Temperature Magnetic Force Microscopy on Single Molecule Magnet-Based Microarrays.

The magnetic properties of some single molecule magnets (SMM) on surfaces can be strongly modified by the molecular packing in nanometric films/aggregates or by interactions with the substrate, which affect the molecular orientation and geometry. Detailed investigations of the magnetism of thin SMM films and nanostructures are necessary for the development of spin-based molecular devices, however this task is challenged by the limited sensitivity of laboratory-based magnetometric techniques and often requires access to synchrotron light sources to perform surface sensitive X-ray magnetic circular dichroism (XMCD) investigations. Here we show that low-temperature magnetic force microscopy is an alternative powerful laboratory tool able to extract the field dependence of the magnetization and to identify areas of in-plane and perpendicular magnetic anisotropy in microarrays of the SMM terbium(III) bis-phthalocyaninato (TbPc2) neutral complex grown as nanosized films on SiO2 and perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), and this is in agreement with data extracted from nonlocal XMCD measurements performed on homogeneous TbPc2/PTCDA films.

Sulfonated NbS2-based proton-exchange membranes for vanadium redox flow batteries.

In this work, novel proton-exchange membranes (PEMs) based on sulfonated poly(ether ether ketone) (SPEEK) and two-dimensional (2D) sulfonated niobium disulphide (S-NbS2) nanoflakes are synthesized by a solution-casting method and used in vanadium redox flow batteries (VRFBs). The NbS2 nanoflakes are produced by liquid-phase exfoliation of their bulk counterpart and chemically functionalized with terminal sulfonate groups to improve dimensional and chemical stabilities, proton conductivity (σ) and fuel barrier properties of the as-produced membranes. The addition of S-NbS2 nanoflakes to SPEEK decreases the vanadium ion permeability from 5.42 × 10-7 to 2.34 × 10-7 cm2 min-1. Meanwhile, it increases the membrane σ and selectivity up to 94.35 mS cm-2 and 40.32 × 104 S min cm-3, respectively. The cell assembled with the optimized membrane incorporating 2.5 wt% of S-NbS2 nanoflakes (SPEEK:2.5% S-NbS2) exhibits high efficiency metrics, i.e., coulombic efficiency between 98.7 and 99.0%, voltage efficiency between 90.2 and 73.2% and energy efficiency between 89.3 and 72.8% within the current density range of 100-300 mA cm-2, delivering a maximum power density of 0.83 W cm-2 at a current density of 870 mA cm-2. The SPEEK:2.5% S-NbS2 membrane-based VRFBs show a stable behavior over 200 cycles at 200 mA cm-2. This study opens up an effective avenue for the production of advanced SPEEK-based membranes for VRFBs.

Topochemical Transformation of Two-Dimensional VSe2 into Metallic Nonlayered VO2 for Water Splitting Reactions in Acidic and Alkaline Media.

The engineering of the structural and morphological properties of nanomaterials is a fundamental aspect to attain desired performance in energy storage/conversion systems and multifunctional composites. We report the synthesis of room temperature-stable metallic rutile VO2 (VO2 (R)) nanosheets by topochemically transforming liquid-phase exfoliated VSe2 in a reductive Ar-H2 atmosphere. The as-produced VO2 (R) represents an example of two-dimensional (2D) nonlayered materials, whose bulk counterparts do not have a layered structure composed by layers held together by van der Waals force or electrostatic forces between charged layers and counterbalancing ions amid them. By pretreating the VSe2 nanosheets by O2 plasma, the resulting 2D VO2 (R) nanosheets exhibit a porous morphology that increases the material specific surface area while introducing defective sites. The as-synthesized porous (holey)-VO2 (R) nanosheets are investigated as metallic catalysts for the water splitting reactions in both acidic and alkaline media, reaching a maximum mass activity of 972.3 A g-1 at -0.300 V vs RHE for the hydrogen evolution reaction (HER) in 0.5 M H2SO4 (faradaic efficiency = 100%, overpotential for the HER at 10 mA cm-2 = 0.184 V) and a mass activity (calculated for a non 100% faradaic efficiency) of 745.9 A g-1 at +1.580 V vs RHE for the oxygen evolution reaction (OER) in 1 M KOH (overpotential for the OER at 10 mA cm-2 = 0.209 V). By demonstrating proof-of-concept electrolyzers, our results show the possibility to synthesize special material phases through topochemical conversion of 2D materials for advanced energy-related applications.

Two-Dimensional Gallium Sulfide Nanoflakes for UV-Selective Photoelectrochemical-type Photodetectors.

Two-dimensional (2D) transition-metal monochalcogenides have been recently predicted to be potential photo(electro)catalysts for water splitting and photoelectrochemical (PEC) reactions. Differently from the most established InSe, GaSe, GeSe, and many other monochalcogenides, bulk GaS has a large band gap of ∼2.5 eV, which increases up to more than 3.0 eV with decreasing its thickness due to quantum confinement effects. Therefore, 2D GaS fills the void between 2D small-band-gap semiconductors and insulators, resulting of interest for the realization of van der Waals type-I heterojunctions in photocatalysis, as well as the development of UV light-emitting diodes, quantum wells, and other optoelectronic devices. Based on theoretical calculations of the electronic structure of GaS as a function of layer number reported in the literature, we experimentally demonstrate, for the first time, the PEC properties of liquid-phase exfoliated GaS nanoflakes. Our results indicate that solution-processed 2D GaS-based PEC-type photodetectors outperform the corresponding solid-state photodetectors. In fact, the 2D morphology of the GaS flakes intrinsically minimizes the distance between the photogenerated charges and the surface area at which the redox reactions occur, limiting electron-hole recombination losses. The latter are instead deleterious for standard solid-state configurations. Consequently, PEC-type 2D GaS photodetectors display a relevant UV-selective photoresponse. In particular, they attain responsivities of 1.8 mA W-1 in 1 M H2SO4 [at 0.8 V vs reversible hydrogen electrode (RHE)], 4.6 mA W-1 in 1 M Na2SO4 (at 0.9 V vs RHE), and 6.8 mA W-1 in 1 M KOH (at 1.1. V vs RHE) under 275 nm illumination wavelength with an intensity of 1.3 mW cm-2. Beyond the photodetector application, 2D GaS-based PEC-type devices may find application in tandem solar PEC cells in combination with other visible-sensitive low-band-gap materials, including transition-metal monochalcogenides recently established for PEC solar energy conversion applications.

Liquid-Phase Exfoliated GeSe Nanoflakes for Photoelectrochemical-Type Photodetectors and Photoelectrochemical Water Splitting.

Photoelectrochemical (PEC) systems represent powerful tools to convert electromagnetic radiation into chemical fuels and electricity. In this context, two-dimensional (2D) materials are attracting enormous interest as potential advanced photo(electro)catalysts and, recently, 2D group-IVA metal monochalcogenides have been theoretically predicted to be water splitting photocatalysts. In this work, we use density functional theory calculations to theoretically investigate the photocatalytic activity of single-/few-layer GeSe nanoflakes for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) in pH conditions ranging from 0 to 14. Our simulations show that GeSe nanoflakes with different thickness can be mixed in the form of nanoporous films to act as nanoscale tandem systems, in which the flakes, depending on their thickness, can operate as HER- and/or OER photocatalysts. On the basis of theoretical predictions, we report the first experimental characterization of the photo(electro)catalytic activity of single-/few-layer GeSe flakes in different aqueous media, ranging from acidic to alkaline solutions: 0.5 M H2SO4 (pH 0.3), 1 M KCl (pH 6.5), and 1 M KOH (pH 14). The films of the GeSe nanoflakes are fabricated by spray coating GeSe nanoflakes dispersion in 2-propanol obtained through liquid-phase exfoliation of synthesized orthorhombic (Pnma) GeSe bulk crystals. The PEC properties of the GeSe nanoflakes are used to design PEC-type photodetectors, reaching a responsivity of up to 0.32 AW-1 (external quantum efficiency of 86.3%) under 455 nm excitation wavelength in acidic electrolyte. The obtained performances are superior to those of several self-powered and low-voltage solution-processed photodetectors, approaching that of self-powered commercial UV-Vis photodetectors. The obtained results inspire the use of 2D GeSe in proof-of-concept water photoelectrolysis cells.

Enhancement of the Magnetic Coupling in Exfoliated CrCl3 Crystals Observed by Low-Temperature Magnetic Force Microscopy and X-ray Magnetic Circular Dichroism.

Magnetic crystals formed by 2D layers interacting by weak van der Waals forces are currently a hot research topic. When these crystals are thinned to nanometric size, they can manifest strikingly different magnetic behavior compared to the bulk form. This can be the result of, for example, quantum electronic confinement effects, the presence of defects, or pinning of the crystallographic structure in metastable phases induced by the exfoliation process. In this work, an investigation of the magnetism of micromechanically cleaved CrCl3 flakes with thickness >10 nm is performed. These flakes are characterized by superconducting quantum interference device magnetometry, surface-sensitive X-ray magnetic circular dichroism, and spatially resolved magnetic force microscopy. The results highlight an enhancement of the CrCl3 antiferromagnetic interlayer interaction that appears to be independent of the flake size when the thickness is tens of nanometers. The estimated exchange field is 9 kOe, representing an increase of ≈900% compared to the one of the bulk crystals. This effect can be attributed to the pinning of the high-temperature monoclinic structure, as recently suggested by polarized Raman spectroscopy investigations in thin (8-35 nm) CrCl3 flakes.

Electrophoretic Deposition of WS2 Flakes on Nanoholes Arrays-Role of Used Suspension Medium.

Here we optimized the electrophoretic deposition process for the fabrication of WS2 plasmonic nanohole integrated structures. We showed how the conditions used for site-selective deposition influenced the properties of the deposited flakes. In particular, we investigated the effect of different suspension buffers used during the deposition both in the efficiency of the process and in the stability of WS2 flakes, which were deposited on an ordered arrays of plasmonic nanostructures. We observed that a proper buffer can significantly facilitate the deposition process, keeping the material stable with respect to oxidation and contamination. Moreover, the integrated plasmonic structures that can be prepared with this process can be applied to enhanced spectroscopies and for the preparation of 2D nanopores.

Site-Selective Integration of MoS2 Flakes on Nanopores by Means of Electrophoretic Deposition.

Here, we propose an easy method for site-selective deposition of two-dimensional (2D) material flakes onto nanoholes by means of electrophoretic deposition. This method can be applied to both simple flat nanostructures and complex three-dimensional structures incorporating nanoholes. The deposition method is here used for the decoration of large ordered arrays of plasmonic structures with either a single or few layers of MoS2. In principle, the plasmonic field generated by the nanohole can significantly interact with the 2D layer leading to enhanced light-material interaction. This makes our platform an ideal system for hybrid 2D material/plasmonic investigations. The engineered deposition of 2D materials on plasmonic nanostructures is useful for several important applications such as enhanced light emission, strong coupling, hot-electron generation, and 2D material sensors.

Self-Assembled Molecular Nanowires for High-Performance Organic Transistors.

While organic semiconductors provide tantalizing possibilities for low-cost, light-weight, flexible electronic devices, their current use in transistors-the fundamental building block-is rather limited as their speed and reliability are not competitive with those of their inorganic counterparts and are simply too poor for many practical applications. Through self-assembly, highly ordered nanostructures can be prepared that have more competitive transport characteristics; however, no simple, scalable method has been discovered that can produce devices on the basis of such nanostructures. Here, we show how transistors of self-assembled molecular nanowires can be fabricated using a scalable, gradient sublimation technique, which have dramatically improved characteristics compared to those of their thin-film counterparts, both in terms of performance and stability. Nanowire devices based on copper phthalocyanine have been fabricated with threshold voltages as low as -2.1 V, high on/off ratios of 105, small subthreshold swings of 0.9 V/decade, and mobilities of 0.6 cm2/V s, and lower trap energies as deduced from temperature-dependent properties, in line with leading organic semiconductors involving more complex fabrication. High-performance transistors manufactured using our scalable deposition technique, compatible with flexible substrates, could enable integrated all-organic chips implementing conventional as well as neuromorphic computation and combining sensors, logic, data storage, drivers, and displays.

Molecular Order in Buried Layers of TbPc2 Single-Molecule Magnets Detected by Torque Magnetometry.

Cantilever torque magnetometry is used to elucidate the orientation of magnetic molecules in thin films. The technique allows depth-resolved investigations by intercalating a layer of anisotropic magnetic molecules in a film of its isotropic analogues. The proof-of-concept is here demonstrated with the single-molecule magnet TbPc2 evidencing also an exceptional long-range templating effect on substrates coated by the organic molecule perylene-3,4,9,10-tetracarboxylic dianhydride.

High-temperature antiferromagnetism in molecular semiconductor thin films and nanostructures.

The viability of dilute magnetic semiconductors in applications is linked to the strength of the magnetic couplings, and room temperature operation is still elusive in standard inorganic systems. Molecular semiconductors are emerging as an alternative due to their long spin-relaxation times and ease of processing, but, with the notable exception of vanadium-tetracyanoethylene, magnetic transition temperatures remain well below the boiling point of liquid nitrogen. Here we show that thin films and powders of the molecular semiconductor cobalt phthalocyanine exhibit strong antiferromagnetic coupling, with an exchange energy reaching 100 K. This interaction is up to two orders of magnitude larger than in related phthalocyanines and can be obtained on flexible plastic substrates, under conditions compatible with routine organic electronic device fabrication. Ab initio calculations show that coupling is achieved via superexchange between the singly occupied a1g () orbitals. By reaching the key milestone of magnetic coupling above 77 K, these results establish quantum spin chains as a potentially useable feature of molecular films.

Temperature- and Light-Induced Spin Crossover Observed by X-ray Spectroscopy on Isolated Fe(II) Complexes on Gold.

Using X-ray absorption techniques, we show that temperature- and light-induced spin crossover properties are conserved for a submonolayer of the [Fe(H2B(pz)2)2(2,2'-bipy)] complex evaporated onto a Au(111) surface. For a significant fraction of the molecules, we see changes in the absorption at the L2,3 edges that are consistent with those observed in bulk and thick film references. Assignment of these changes to spin crossover is further supported by multiplet calculations to simulate the X-ray absorption spectra. As others have observed in experiments on monolayer coverages, we find that many molecules in our submonolayer system remain pinned in one of the two spin states. Our results clearly demonstrate that temperature- and light-induced spin crossover is possible for isolated molecules on surfaces but that interactions with the surface may play a key role in determining when this can occur.