Plasmon-assisted spin transition in gold nanostar@spin crossover heterostructures

Aquí presentamos el diseño de nanopartículas core@shell formadas por un núcleo de nanoestrella de Au metálico y una capa cruzada de espín basada en el polímero de coordinación [Fe(Htrz)2(trz)](BF4). Este procedimiento es general y se ha extendido a otras morfologías metálicas (nanovarillas, nanotriángulos). Gracias al efecto fototérmico derivado de las propiedades plasmónicas de la nanoestrella de Au, el 60 % de los centros de hierro experimentan una transición de espín térmico dentro de la histéresis térmica provocada por una irradiación de baja intensidad con un láser de 808 nm. En comparación con otras morfologías de Au, la gran ventaja de la forma de nanoestrella surge de los puntos cal…

The design of magneto-plasmonic nanostructures formed by magnetic Prussian Blue-type nanocrystals decorated with Au nanoparticles.

Abstract: We have developed a general protocol for the preparation of hybrid nanostructures formed by nanoparticles (NPs) of molecule-based magnets based on Prussian Blue Analogues (PBAs) decorated with plasmonic Au NPs of different shapes. By adjusting the pH, Au NPs can be attached preferentially along the edges of the PBA or randomly on the surface. The protocol allows tuning the plasmonic properties of the hybrids in the whole visible spectrum.

New Molecular-Based Materials for Enabling Electro-Optical Bistability in the Silicon Photonics Platform

Electro-optical bistability is a functionality which can be crucial for a wide range of applications as it can enable non-volatile and ultra-low power switching performance. We investigate the integration of a molecular-based material presenting a Spin Crossover (SCO) effect in the silicon platform for enabling optical bistability. The SCO phenomenon involves a switching process between two molecular spin states. This spin transition comes along with a change in the optical refractive index that can be switched by different external stimuli such as a variation of temperature or light irradiation and which has a hysteretic behaviour. The SCO material can be synthetized as nanoparticles so th…

Charge Mobility and Dynamics in Spin-Crossover Nanoparticles Studied by Time-Resolved Microwave Conductivity

We use the electrode-less time-resolved microwave conductivity (TRMC) technique to characterize spin-crossover (SCO) nanoparticles. We show that TRMC is a simple and accurate mean for simultaneously as-sessing the magnetic state of SCO compounds and charge transport information on the nanometre length scale. In the low-spin state from liquid nitrogen temperature up to 360 K the TRMC measurements present two well-defined regimes in the mobility and in the half-life times, possessing similar transition tempera-tures TR near 225 K. Below TR, an activation-less regime associated with short lifetimes of the charge carri-ers points at the presence of shallow-trap states. Above TR, these states ar…

Fast Polymeric Functionalization Approach for the Covalent Coating of MoS2 Layers

We present the covalent coating of chemically exfoliated molybdenum disulfide (MoS2) based on the polymerization of functional acryl molecules. The method relies on the efficient diazonium anchoring reaction to provoke the in situ radical polymerization and covalent adhesion of functional coatings. In particular, we successfully implement hydrophobicity on the exfoliated MoS2 in a direct, fast, and quantitative synthetic approach. The covalent functionalization is proved by multiple techniques including X-ray photoelectron spectroscopy and TGA-MS. This approach represents a simple and general protocol to reach dense and homogeneous functional coatings on 2D materials.

Reinforced Room-Temperature Spin Filtering in Chiral Paramagnetic Metallopeptides

Chirality-induced spin selectivity (CISS), whereby helical molecules polarize the spin of electrical current, is an intriguing effect with potential applications in nanospintronics. In this nascent field, the study of the CISS effect using paramagnetic chiral molecules, which could introduce another degree of freedom in controlling the spin transport, remains so far unexplored. To address this challenge, herein we propose the use of self-assembled monolayers (SAMs) of helical lanthanide-binding peptides. To elucidate the effect of the paramagnetic nuclei, monolayers of the peptide coordinating paramagnetic or diamagnetic ions are prepared. By means of spin-dependent electrochemistry, the CI…

Sensing of the Molecular Spin in Spin-Crossover Nanoparticles with Micromechanical Resonators

In the past years, the use of highly sensitive silicon microelectromechanical cantilevers has been proposed as a tool to characterize the spin-crossover phenomenon by employing fast optical readout of the motion. In this work, Fe II -based spin-crossover nanoparticles of the well-known [Fe(Htrz) 2 (trz)](BF 4 ) complex wrapped with thin silica shells of different sizes will be studied by means of silicon microresonators. The silica shell will enhance its chemical stability, whereas the low thickness will allow a proper mechanical coupling between the cantilever and the spin-crossover core. To maximize the sensing of the spin-crossover phenomena, different cantilever geometries and flexural…

Molecular stabilization of chemically exfoliated bare MnPS3 layers

Transition metal chalcogenophosphates of general formula MPX3 have attracted recent interest in the field of 2D materials due to the possibility of tuning their properties when reaching the 2D limit. Several works address this challenge by dry mechanical exfoliation. However, only a few of them use a scalable approach. In this work, we apply a general chemical protocol to exfoliate MnPS3. The method uses in a first step chemical intercalation and liquid phase exfoliation, followed in a second step by the addition of molecules used as capping agents on the inorganic layers. Therefore, molecules of different nature prompts the quality of the exfoliated material and its stabilization in aqueou…

Downsizing of robust Fe-triazole@SiO2 spin-crossover nanoparticles with ultrathin shells

A chemical protocol to design robust hybrid [Fe(Htrz)2(trz)](BF4)@SiO2 nanoparticles (NPs) with sizes as small as 28 nm and ultrathin silica shells below 3 nm has been developed. These NPs present a characteristic abrupt spin transition with a subsequent decrease in the width of the thermal hysteresis upon reducing the NP size.

Design of Bistable Gold@Spin‐Crossover Core–Shell Nanoparticles Showing Large Electrical Responses for the Spin Switching

<p>A simple protocol to prepare core-shell gold@spin-crossover (Au@SCO) nanoparticles (NPs) based on the 1D spin-crossover [Fe(Htrz)<sub>2</sub>(trz)](BF<sub>4</sub>) coordination polymer is reported. The synthesis relies on a two-step approach consisting on a partial surface ligand substitution of the citrate-stabilized Au NPs followed by the controlled growth of a very thin layer of the SCO polymer. As a result, colloidally stable core@shell spherical NPs of 19 nm in size exhibiting a narrow distribution in sizes have been obtained, revealing a switchable SCOshell of <i>ca.</i>4 nm. Temperature-dependent charge transport measurements of an electri…

Size-Dependent Spin Switching in Robust Fe-triazole@SiO2 Spin-Crossover Nanoparticles with Ultrathin Shell

<p>A familly of chemically robust hybrid [Fe(Htrz)2(trz)](BF4)@SiO2nanoparticles (NPs) presenting different sizes (from ca. 90 to 28 nm) and an ultrathin silica shell (< 3 nm) have been prepared. All NPs present a characteristic abrupt spin transition with a subsequent decrease in the width of the thermal hysteresis upon reducing the NP size.<br></p>

Near Room-Temperature Memory Devices Based on Hybrid Spin-Crossover@SiO2Nanoparticles Coupled to Single-Layer Graphene Nanoelectrodes

The charge transport properties of SCO [Fe(Htrz)2 (trz)](BF4 ) NPs covered with a silica shell placed in between single-layer graphene electrodes are reported. A reproducible thermal hysteresis loop in the conductance above room-temperature is evidenced. This bistability combined with the versatility of graphene represents a promising scenario for a variety of technological applications but also for future sophisticated fundamental studies.

Core–Shell Nanoparticles: Design of Bistable Gold@Spin‐Crossover Core–Shell Nanoparticles Showing Large Electrical Responses for the Spin Switching (Adv. Mater. 27/2019)

Self-assembled monolayers on a ferromagnetic permalloy surface.

Self-assembled monolayers (SAMs) are nowadays broadly used as surface protectors or modifiers and play a key role in many technological applications. This has motivated the study of their formation in all kind of materials; however, and despite the current interest in molecular spintronics, the study of SAMs on ferromagnetic surfaces remains almost unexplored. In this paper, we report for the first time a methodology for the formation of SAMs of n-alkylphosphonic acids on permalloy in ambient conditions. The formed monolayers have been fully characterized by means of contact angle measurements, atomic force microscopy, X-ray photoelectron spectroscopy, matrix assisted laser desorption ioniz…

Halide-Mediated Modification of Magnetism and Electronic Structure of α-Co(II) Hydroxides: Synthesis, Characterization, and DFT+U Simulations.

The present study introduces a comprehensive exploration in terms of physicochemical characterization and calculations based on density functional theory with Hubbard's correction (DFT+U) of the whole family of α-Co(II) hydroxyhalide (F, Cl, Br, I). These samples were synthesized at room temperature by employing a one-pot approach based on the epoxide route. A thorough characterization (powder X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetric analysis/mass spectroscopy, and magnetic and conductivity measurements) corroborated by simulation is presented that analyzes the structural, magnetic, and electronic aspects. Beyond the inherent tendency of intercalated anions to …

Smart molecular/MoS2 Heterostructures Featuring Light and Thermally-Induced Strain Driven by Spin Switching

In this work we exploit the ability of spin-crossover molecules to switch between two spin states, upon the application of external stimuli, to prepare smart molecular/2D heterostructures. Through the chemical design of the hybrid interface, that involves a covalent grafting between the two components, we obtain a hybrid heterostructure formed by spin-crossover nanoparticles anchored on chemically functionalized monolayers of semiconducting MoS2. In the resulting hybrid, the strain generated by the molecular system over the MoS2 layer, as a consequence of a thermal or light-induced spin switching, results in a dramatic and reversible change of its electrical and optical properties. This nov…

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 spi…