Engineering On‐Surface Spin Crossover: Spin‐State Switching in a Self‐Assembled Film of Vacuum‐Sublimable Functional Molecule

The realization of spin‐crossover (SCO)‐based applications requires study of the spin‐state switching characteristics of SCO complex molecules within nanostructured environments, especially on surfaces. Except for a very few cases, the SCO of a surface‐bound thin molecular film is either quenched or heavily altered due to: (i) molecule–surface interactions and (ii) differing intermolecular interactions in films relative to the bulk. By fabricating SCO complexes on a weakly interacting surface, the interfacial quenching problem is tackled. However, engineering intermolecular interactions in thin SCO active films is rather difficult. Here, a molecular self‐assembly strategy is proposed to fabricate thin spin‐switchable surface‐bound films with programmable intermolecular interactions. Molecular engineering of the parent complex system [Fe(H₂B(pz)₂)₂(bpy)] (pz = pyrazole, bpy = 2,2′‐bipyridine) with a dodecyl (C₁₂) alkyl chain yields a classical amphiphile‐like functional and vacuum‐sublimable charge‐neutral Fe^II complex, [Fe(H₂B(pz)₂)₂(C₁₂‐bpy)] (C₁₂‐bpy = dodecyl[2,2′‐bipyridine]‐5‐carboxylate). Both the bulk powder and 10 nm thin films sublimed onto either quartz glass or SiO_x surfaces of the complex show comparable spin‐state switching characteristics mediated by similar lamellar bilayer like self‐assembly/molecular interactions. This unprecedented observation augurs well for the development of SCO‐based applications, especially in molecular spintronics.     

Microwave Energy Drives “On–Off–On” Spin‐Switch Behavior in Nitrogen‐Doped Graphene

The established application of graphene in organic/inorganic spin‐valve spintronic assemblies is as a spin‐transport channel for spin‐polarized electrons injected from ferromagnetic substrates. To generate and control spin injection without such substrates, the graphene backbone must be imprinted with spin‐polarized states and itinerant‐like spins. Computations suggest that such states should emerge in graphene derivatives incorporating pyridinic nitrogen. The synthesis and electronic properties of nitrogen‐doped graphene (N content: 9.8%), featuring both localized spin centers and spin‐containing sites with itinerant electron properties, are reported. This material exhibits spin‐switch behavior (on–off–on) controlled by microwave irradiation at X‐band frequency. This phenomenon may enable the creation of novel types of switches, filters, and spintronic devices using sp²‐only 2D systems.     

Organic Spin‐Valves and Beyond: Spin Injection and Transport in Organic Semiconductors and the Effect of Interfacial Engineering

Since the first observation of the spin‐valve effect through organic semiconductors, efforts to realize novel spintronic technologies based on organic semiconductors have been rapidly growing. However, a complete understanding of spin‐polarized carrier injection and transport in organic semiconductors is still lacking and under debate. For example, there is still no clear understanding of major spin‐flip mechanisms in organic semiconductors and the role of hybrid metal–organic interfaces in spin injection. Recent findings suggest that organic single crystals can provide spin‐transport media with much less structural disorder relative to organic thin films, thus reducing momentum scattering. Additionally, modification of the band energetics, morphology, and even spin magnetic moment at the metal–organic interface by interface engineering can greatly impact the efficiency of spin‐polarized carrier injection. Here, progress on efficient spin‐polarized carrier injection into organic semiconductors from ferromagnetic metals by using various interface engineering techniques is presented, such as inserting a metallic interlayer, a molecular self‐assembled monolayer (SAM), and a ballistic carrier emitter. In addition, efforts to realize long spin transport in single‐crystalline organic semiconductors are discussed. The focus here is on understanding and maximizing spin‐polarized carrier injection and transport in organic semiconductors and insight is provided for the realization of emerging organic spintronics technologies.     

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

A simple chemical protocol to prepare core–shell gold@spin‐crossover (Au@SCO) nanoparticles (NPs) based on the 1D spin‐crossover [Fe(Htrz)₂(trz)](BF₄) coordination polymer is reported. The synthesis relies on a two‐step approach consisting of 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 with a Au core of ca. 12 nm and a thin SCO shell 4 nm thick, are obtained, exhibiting a narrow distribution in sizes. Differential scanning calorimetry proves that a cooperative spin transition in the range 340–360 K is maintained in these Au@SCO NPs, in full agreement with the values reported for pristine 4 nm SCO NPs. Temperature‐dependent charge‐transport measurements of an electrical device based on assemblies of these Au@SCO NPs also support this spin transition. Thus, a large change in conductance upon spin state switching, as compared with other memory devices based on the pristine SCO NPs, is detected. This results in a large improvement in the sensitivity of the device to the spin transition, with values for the ON/OFF ratio which are an order of magnitude better than the best ones obtained in previous SCO devices.     

Spin–Orbit Torque Switching in a Nearly Compensated Heusler Ferrimagnet

Ferrimagnetic materials combine the advantages of the low magnetic moment of an antiferromagnet and the ease of realizing magnetic reading of a ferromagnet. Recently, it was demonstrated that compensated ferrimagnetic half metals can be realized in Heusler alloys, where high spin polarization, zero magnetic moment, and low magnetic damping can be achieved at the same time. In this work, by studying the spin–orbit torque induced switching in the Heusler alloy Mn₂Ru_{1? x} Ga, it is found that efficient current‐induced magnetic switching can be realized in a nearly compensated sample with strong perpendicular anisotropy and large film thickness. This work demonstrates the possibility of employing compensated Heusler alloys for fast, energy‐efficient spintronic devices.     

Electrical Detection of Spin Precession in Freely Suspended Graphene Spin Valves on Cross‐Linked Poly(methyl methacrylate)

Spin injection and detection is achieved in freely suspended graphene using cobalt electrodes and a nonlocal spin‐valve geometry. The devices are fabricated with a single electron‐beam‐resist poly(methyl methacrylate) process that minimizes both the fabrication steps and the number of (aggressive) chemicals used, greatly reducing contamination and increasing the yield of high‐quality, mechanically stable devices. As‐grown devices can present mobilities exceeding 10⁴ cm² V^?1 s^?1 at room temperature and, because the contacts deposited on graphene are only exposed to acetone and isopropanol, the method is compatible with almost any contacting material. Spin accumulation and spin precession are studied in these nonlocal spin valves. Fitting of Hanle spin precession data in bilayer and multilayer graphene yields a spin relaxation time of ～125‐250 ps and a spin diffusion length of 1.7‐1.9 μm at room temperature.     

Magnetic Susceptibility Study of Sub‐Pico‐emu Sample Using a Micromagnetometer: An Investigation through Bistable Spin‐Crossover Materials

A promising and original method to study the spin‐transition in bistable spin‐crossover (SCO) materials using a magnetoresistive multiring sensor and its self‐generated magnetic field is reported. Qualitative and quantitative studies are carried out combining theoretical and experimental approaches. The results show that only a small part of matter dropped on the sensor surface is probed by the device. At a low bias‐current range, the number of detected nanoparticles depends on the amplitude of the current. However, in agreement with the theoretical model, the stray voltage from the particles is proportional to the current squared. By changing both the bias current and the concentration of particle droplet, the thermal hysteresis of an ultrasmall volume, 1 × 10^?4 mm³, of SCO particles is measured. The local probe of the experimental setup allows a highest resolution of 4 × 10^?14 emu to be reached, which is never achieved by experimental methods at room temperature.     

Variations in BOLD response latency estimated from event‐related fMRI at 3T: Comparisons between gradient‐echo and Spin‐echo

Functional magnetic resonance imaging (fMRI) commonly uses gradient‐recalled echo (GRE) signals to detect regional hemodynamic variations originating from neural activities. While the spatial localization of activation shows promising applications, indexing temporal response remains a poor mechanism for detecting the timing of neural activity. Particularly, the hemodynamic response may fail to resolve sub‐second temporal differences between brain regions because of its signal origin or noise in data, or both. This study aimed at evaluating the performance of latency estimation using different fMRI techniques, with two event‐related experiments at 3T. Experiment I evaluated latency variations within the visual cortex and their relationship with contrast‐to‐noise ratios (CNRs) for GRE, spin echo (SE), and diffusion‐weighted SE (DWSE). Experiment II used delayed visual stimuli between two hemifields (delay time = 0, 250, and 500 ms, respectively) to assess the temporal resolving power of three protocols: GRE_TR1000, GRE_TR500, and SE_TR1000. The results of experiment I showed the earliest latency with DWSE, followed by SE, and then GRE. Latency variations decreased as CNR increased. However, similar variations were found between GRE and SE, when the latter had lower CNR. In experiment II, measured stimulus delays from all conditions were significantly correlated with preset stimulus delays. Inter‐subject variation in the measured delay was found to be greatest with GRE_TR1000, followed by GRE_TR500, and the least with SE_TR1000. Conclusively, blood oxygenation level‐dependent responses obtained from GRE exhibit greater CNR but no compromised latency variations in the visual cortex. SE is potentially capable of improving the performance of latency estimation, especially for group analysis. © 2013 Wiley Periodicals, Inc. Int J Imaging Syst Technol, 23, 215–221, 2013