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…

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…

Phase Transitions in Spin-Crossover Thin Films Probed by Graphene Transport Measurements

Future multi-functional hybrid devices might combine switchable molecules and 2D material-based devices. Spin-crossover compounds are of particular interest in this context since they exhibit bistability and memory effects at room temperature while responding to numerous external stimuli. Atomically-thin 2D materials such as graphene attract a lot of attention for their fascinating electrical, optical, and mechanical properties, but also for their reliability for room-temperature operations. Here, we demonstrate that thermally-induced spin-state switching of spin-crossover nanoparticle thin films can be monitored through the electrical transport properties of graphene lying underneath the f…

Spin switching in electronic devices based on 2D assemblies of spin-crossover nanoparticles

In this communication we study the transport properties of two-dimensional assemblies of [Fe(Htrz)2(trz)](BF4) spin-crossover nanoparticles (NPs) with two different morphologies. The NPs have been synthesized made in a similar manner than in our previous study in which single NPs were measured. We prepared free-standing self-assembled monolayer sheets of both SCO NPs formed at the air/liquid interface on holey carbon TEM grids to extract their global arrangement and NP size distributions by STEM-HAADF technique. The SCO NP systems present a rod-like shape and possess two different volumes, corresponding to lengths of 25 nm and 44 nm along the rod direction and average diameters of 10 nm and…

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…

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)

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…