Interplay between Optical Emission and Magnetism in the van der Waals Magnetic Semiconductor CrSBr in the Two-Dimensional Limit.

The van der Waals semiconductor metamagnet CrSBr offers an ideal platform for studying the interplay between optical and magnetic properties in the two-dimensional limit. Here, we carried out an exhaustive optical characterization of this material by means of temperature- and magnetic-field-dependent photoluminescence (PL) on flakes of different thicknesses down to the monolayer. We found a characteristic emission peak that is quenched upon switching the ferromagnetic layers from an antiparallel to a parallel configuration and exhibits a temperature dependence different from that of the peaks commonly ascribed to excitons. The contribution of this peak to the PL is boosted around 30-40 K, coinciding with the hidden order magnetic transition temperature. Our findings reveal the connection between the optical and magnetic properties via the ionization of magnetic donor vacancies. This behavior enables a useful tool for the optical reading of the magnetic states in atomically thin layers of CrSBr and shows the potential of the design of 2D heterostructures with magnetic and excitonic properties.

Hexagonal Hybrid Bismuthene by Molecular Interface Engineering.

High-quality devices based on layered heterostructures are typically built from materials obtained by complex solid-state physical approaches or laborious mechanical exfoliation and transfer. Meanwhile, wet-chemically synthesized materials commonly suffer from surface residuals and intrinsic defects. Here, we synthesize using an unprecedented colloidal photocatalyzed, one-pot redox reaction a few-layers bismuth hybrid of "electronic grade" structural quality. Intriguingly, the material presents a sulfur-alkyl-functionalized reconstructed surface that prevents it from oxidation and leads to a tuned electronic structure that results from the altered arrangement of the surface. The metallic behavior of the hybrid is supported by ab initio predictions and room temperature transport measurements of individual nanoflakes. Our findings indicate how surface reconstructions in two-dimensional (2D) systems can promote unexpected properties that can pave the way to new functionalities and devices. Moreover, this scalable synthetic process opens new avenues for applications in plasmonics or electronic (and spintronic) device fabrication. Beyond electronics, this 2D hybrid material may be of interest in organic catalysis, biomedicine, or energy storage and conversion.

Photoluminescence Enhancement by Band Alignment Engineering in MoS2/FePS3 van der Waals Heterostructures.

Single-layer semiconducting transition metal dichalcogenides (2H-TMDs) display robust excitonic photoluminescence emission, which can be improved by controlled changes to the environment and the chemical potential of the material. However, a drastic emission quench has been generally observed when TMDs are stacked in van der Waals heterostructures, which often favor the nonradiative recombination of photocarriers. Herein, we achieve an enhancement of the photoluminescence of single-layer MoS2 on top of van der Waals FePS3. The optimal energy band alignment of this heterostructure preserves light emission of MoS2 against nonradiative interlayer recombination processes and favors the charge transfer from MoS2, an n-type semiconductor, to FePS3, a p-type narrow-gap semiconductor. The strong depletion of carriers in the MoS2 layer is evidenced by a dramatic increase in the spectral weight of neutral excitons, which is strongly modulated by the thickness of the FePS3 underneath, leading to the increase of photoluminescence intensity. The present results demonstrate the potential for the rational design of van der Waals heterostructures with advanced optoelectronic properties.

Spin-crossover nanoparticles anchored on MoS2 layers for heterostructures with tunable strain driven by thermal or light-induced spin switching.

In the past few years, the effect of strain on the optical and electronic properties of MoS2 layers has attracted particular attention as it can improve the performance of optoelectronic and spintronic devices. Although several approaches have been explored, strain is typically externally applied on the two-dimensional material. In this work, we describe the preparation of a reversible 'self-strainable' system in which the strain is generated at the molecular level by one component of a MoS2-based composite material. Spin-crossover nanoparticles were covalently grafted onto functionalized layers of semiconducting MoS2 to form a hybrid heterostructure. Their ability to switch between two spin states on applying an external stimulus (light irradiation or temperature change) serves to generate strain over the MoS2 layer. A volume change accompanies this spin crossover, and the created strain induces a substantial and reversible change of the electrical and optical properties of the heterostructure.

Mirror effect in atomic force microscopy profiles enables tip reconstruction.

In this work, the tip convolution effect in atomic force microscopy is revisited to illustrate the capabilities of cubic objects for determination of the tip shape and size. Using molecular-based cubic nanoparticles as a reference, a two-step tip reconstruction process has been developed. First, the tip-to-face angle is estimated by means of an analysis of the convolution error while the tip radius is extracted from the experimental profiles. The results obtained are in good agreement with specification of the tip supplier even though the experiments have been conducted using real distribution of nanoparticles with dispersion in size and aspect ratio. This demonstrates the reliability of our method and opens the door for a more accurate tip reconstruction by using calibration standards.

Slow relaxation of the magnetization, reversible solvent exchange and luminescence in 2D anilato-based frameworks.

A series of multifunctional 2D frameworks prepared with Dy(iii) and the bromanilato ligand, formulated as: [Dy2(C6O4Br2)3(G)n]·nG with G = H2O, dimethylformamide (dmf) and dimethylsulfoxide (dmso), can exchange the coordinated and non-coordinated solvent molecules (G) in a reversible way. These multifunctional frameworks show field induced slow relaxation of the magnetization and luminescence that can be easily and reversibly modified by solvent exchange.

WS2 /MoS2 Heterostructures through Thermal Treatment of MoS2 Layers Electrostatically Functionalized with W3 S4 Molecular Clusters.

The preparation of 2D stacked layers combining flakes of different nature gives rise to countless numbers of heterostructures where new band alignments, defined at the interfaces, control the electronic properties of the system. Among the large family of 2D/2D heterostructures, the one formed by the combination of the most common semiconducting transition metal dichalcogenides, WS2 /MoS2 , has awakened great interest owing to its photovoltaic and photoelectrochemical properties. Solution as well as dry physical methods have been developed to optimize the synthesis of these heterostructures. Here, a suspension of negatively charged MoS2 flakes is mixed with a methanolic solution of a cationic W3 S4 -core cluster, giving rise to a homogeneous distribution of the clusters over the layers. In a second step, a calcination of this molecular/2D heterostructure under N2 leads to the formation of clean WS2 /MoS2 heterostructures, where the photoluminescence of both counterparts is quenched, proving an efficient interlayer coupling. Thus, this chemical method combines the advantages of a solution approach (simple, scalable, and low-cost) with the good quality interfaces reached by using more complicated traditional physical methods.

A Local Study of the Transport Mechanisms in MoS2 Layers for Magnetic Tunnel Junctions.

MoS2-based vertical spintronic devices have attracted an increasing interest thanks to theoretical predictions of large magnetoresistance signals. However, experimental performances are still far from expectations. Here, we carry out the local electrical characterization of thin MoS2 flakes in a Co/Al2O3/MoS2 structure through conductive tip AFM measurements. We show that thin MoS2 presents a metallic behavior with a strong lateral transport contribution that hinders the direct tunnelling through thin layers. Indeed, no resistance dependence is observed with the flake thickness. These findings reveal a spin depolarization source in the MoS2-based spin valves, thus pointing to possible solutions to improve their spintronic properties.

A fluorescent layered oxalato-based canted antiferromagnet.

We report the synthesis and characterization of the first fluorescent oxalato-based canted antiferromagnet. Compound [DOC][MnFe(C2O4)3] (1) (DOC = 3,3'-diethyloxacarbocyanine) combines the well-known canted antiferromagnetic [MnFe(C2O4)3]- honeycomb layers with a fluorescent cationic cyanine-type fluorescent dye. Besides the expected spin canted antiferromagnetic order in the oxalato layer at ca. 29 K, we show the key role played by the anionic oxalato lattice in the optical properties of the cation since it provides isolation of dye cations in the hexagonal cavities of the oxalato-based matrix. The emission of the DOC+ dye shows a redshift and a broadening of the emission as well as an increase in the lifetime compared to the emission of the DOC+ cations in solution. These facts are attributed to the isolation effect of the oxalato-based matrix.

Nonanuclear Spin-Crossover Complex Containing Iron(II) and Iron(III) Based on a 2,6-Bis(pyrazol-1-yl)pyridine Ligand Functionalized with a Carboxylate Group.

The synthesis and magnetostructural characterization of [Fe(III)3(µ3-O)(H2O)3[Fe(II)(bppCOOH)(bppCOO)]6](ClO4)13·(CH3)2CO)6·(solvate) (2) are reported. This compound is obtained as a secondary product during synthesis of the mononuclear complex [Fe(II)(bppCOOH)2](ClO4)2 (1). The single-crystal X-ray diffraction structure of 2 shows that it contains the nonanuclear cluster of the formula [Fe(III)3(µ3-O)(H2O)3[Fe(II)(bppCOOH)(bppCOO)]6](13+), which is formed by a central Fe(III)3O core coordinated to six partially deprotonated [Fe(II)(bppCOOH)(bppCOO)](+) complexes. Raman spectroscopy studies on single crystals of 1 and 2 have been performed to elucidate the spin and oxidation states of iron in 2. These studies and magnetic characterization indicate that most of the iron(II) complexes of 2 remain in the low-spin (LS) state and present a gradual and incomplete spin crossover above 300 K. On the other hand, the Fe(III) trimer shows the expected antiferromagnetic behavior. From the structural point of view, 2 represents the first example in which bppCOO(-) acts as a bridging ligand, thus forming a polynuclear magnetic complex.

Correction of the tip convolution effects in the imaging of nanostructures studied through scanning force microscopy.

AFM images are always affected by artifacts arising from tip convolution effects, resulting in a decrease in the lateral resolution of this technique. The magnitude of such effects is described by means of geometrical considerations, thereby providing better understanding of the convolution phenomenon. We demonstrate that for a constant tip radius, the convolution error is increased with the object height, mainly for the narrowest motifs. Certain influence of the object shape is observed between rectangular and elliptical objects with the same height. Such moderate differences are essentially expected among elongated objects; in contrast they are reduced as the object aspect ratio is increased. Finally, we propose an algorithm to study the influence of the size, shape and aspect ratio of different nanometric motifs on a flat substrate. Indeed, with this algorithm, convolution artifacts can be extended to any kind of motif including real surface roughness. From the simulation results we demonstrate that in most cases the real motif's width can be estimated from AFM images without knowing its shape in detail.

Two-color single-photon emission from InAs quantum dots: toward logic information management using quantum light.

In this work, we propose the use of the Hanbury-Brown and Twiss interferometric technique and a switchable two-color excitation method for evaluating the exciton and noncorrelated electron-hole dynamics associated with single photon emission from indium arsenide (InAs) self-assembled quantum dots (QDs). Using a microstate master equation model we demonstrate that our single QDs are described by nonlinear exciton dynamics. The simultaneous detection of two-color, single photon emission from InAs QDs using these nonlinear dynamics was used to design a NOT AND logic transference function. This computational functionality combines the advantages of working with light/photons as input/output device parameters (all-optical system) and that of a nanodevice (QD size of ∼ 20 nm) while also providing high optical sensitivity (ultralow optical power operational requirements). These system features represent an important and interesting step toward the development of new prototypes for the incoming quantum information technologies.

Purcell effect in photonic crystal microcavities embedding InAs/InP quantum wires.

The spontaneous emission rate and Purcell factor of self-assembled quantum wires embedded in photonic crystal micro-cavities are measured at 80 K by using micro-photoluminescence, under transient and steady state excitation conditions. The Purcell factors fall in the range 1.1 - 2 despite the theoretical prediction of ≈15.5 for the figure of merit. We explain this difference by introducing a polarization dependence on the cavity orientation, parallel or perpendicular with respect to the wire axis, plus spectral and spatial detuning factors for the emitters and the cavity modes, taking in account the finite size of the quantum wires.

Au-PVA nanocomposite negative resist for one-step three-dimensional e-beam lithography.

Au nanoparticles are synthesized in situ upon the electron beam exposure of a poly(vinyl alcohol) (PVA) thin film containing Au(III). The e-beam-irradiated areas are insoluble in water (negative-tone resist), and Au-PVA nanocomposite patterns with a variable profile along the structure can be thus generated (3D lithography) in a single step. A local characterization of the generated patterns is performed by high-resolution transmission electron microscopy and UV-vis localized surface plasmon resonance microspectroscopy. This characterization confirms the presence of crystalline nanoparticles and aggregates.