Spin-dependent tunneling and Coulomb blockade in ferromagnetic nanoparticles

In this paper we review studies on spin-dependent transport in systems containing ferromagnetic nanoparticles. In a tunnel junction with a nanometer-scale-island, the charging effect leads to an electric current blockade phenomenon in which a single electron charge plays a significant role in electron transport, resulting in single-electron tunneling (SET) properties such as Coulomb blockade and Coulomb staircase. In a tunnel junction with a ferromagnetic nano-island and electrode, it was expected that the interplay of spin-dependent tunneling (SDT) and SET, i.e., spin-dependent single-electron tunneling (SD-SET), would give rise to remarkable tunnel magnetoresistance (TMR) phenomena. We investigated magnetotransport properties in both sequential tunneling and cotunneling regimes of SET and found the enhancement and oscillation of TMR. The self-assembled ferromagnetic nanoparticles we have employed in this study consisted of a Co–Al–O granular film with cobalt nanoparticles embedded in an Al–O insulating matrix. A _Co36Al22O42${\mathrm{Co}}_{36}{\mathrm{Al}}_{22}{\mathrm{O}}_{42}$ film prepared by a reactive sputtering method produced a TMR ratio reaching 10% and superparamagnetic behavior at room temperature. The TMR ratio exhibited an anomalous increase at low temperatures but no indication of change with bias voltage. In Section 4, we show that the anomalous increase of the MR provided evidence for higher-order tunneling (cotunneling) between large granules through intervening small granules. We emphasize that the existence of higher-order tunneling is a natural consequence of the granular structure, since broad distribution of granule size is an intrinsic property of granular systems. In Section 5, we concentrate on SD-SET properties in sequential tunneling regimes. We fabricated two types of device structures with Co–Al–O film using focused ion-beam milling or electron-beam lithography techniques. One had a granular nanobridge structure: point-shaped electrodes separated by a very narrow lateral gap filled with the Co–Al–O granular film. The other had a current-perpendicular-to-plane (CPP) geometry structure: a thin Co–Al–O granular film sandwiched by ferromagnetic electrodes with the current flowing in the direction perpendicular to the film plane through a few Co particles. We found the enhancement and oscillation of TMR due to spin-dependent SET in sequential tunneling regimes. In Section 6, we report experimental evidence of a spin accumulation effect in Co nanoparticles leading to the oscillation of TMR with alternate sign changes. Furthermore, we discovered that the spin relaxation time in the nanoparticles is unprecedentedly enhanced up to the order of more than hundreds of nanoseconds, compared to that evaluated from the spin-diffusion length of ferromagnetic layers in previous CPP-GMR studies, i.e., the order of tens of picoseconds.     

Basins and bifurcations of a delayed feedback control system and its experimental verification for a DC bus circuit

Nonlinear Dynamics - Stochastic synchrony, also known as noise-induced synchronization that leads to phase coherence, arises when a set of uncoupled neurons synchronizes to a common white noise...     

Synthesis and Bowl-in-Bowl Assembly of a Geodesic Phenylene Bowl

A phenylene multiring with a corannulenoidal skeleton was synthesized. Geodesic constraints over 20 phenylene panels resulted in its nanometer-sized, bowl-shaped molecular structure, which was unequivocally revealed by crystallographic analysis. The crystal structure also showed the presence of a bowl-in-bowl dimeric assembly, which was driven by entropic factors in solution.     

Three-in-One: Miniature Models of Natural Acyl-Transfer Systems Enable Vector-Selective Reaction on the Primary Side of Cyclodextrins

Miniature models of acyl-transfer systems in cells, which were composed by replacing the protein, coenzyme, and substrate with CD, functional group, and CD, respectively, and combining them all together in one, displayed definite role-sharing and exact cooperation of the functional groups and hydrophobic cavity, and thus enabled the regio-specific reaction.     

Synthesis of a Hemispherical Geodesic Phenine Framework by a Polygon Assembling Strategy

A synthetic strategy to construct large geodesic structures of phenine (1,3,5‐trisubstituted benzene) was devised. In this strategy, five pentagons were assembled on an omphalos pentagon, and bridging peripheral pentagons furnished five additional hexagons. Thirty phenine units were synthetically assembled to afford a large C₂₂₀H₁₈₀ molecule with a phenine framework isoreticular to a hemispherical, bisected segment of C₆₀. Although a hemispherical structure of the phenine framework was suggested by solution‐phase NMR spectra, crystallographic analysis revealed an oval‐like deformation of the molecular shape. In‐depth structural analyses, including theoretical calculations, showed that structural fluctuations observed as variations in the biaryl torsion angles allowed structural deformations and, at the same time, that the dynamic fluctuations resulted in the spectroscopic observation of a hemisphere as a time‐averaged structure.     

One-Step Preparation of Fe/N/C Single-Atom Catalysts Containing Fe−N4 Sites from an Iron Complex Precursor with 5,6,7,8-Tetraphenyl-1,12-Diazatriphenylene Ligands

Fe/N/C single-atom catalysts containing Fe−N_x sites prepared by pyrolysis are promising cathode materials for fuel cells and metal-air batteries due to their high oxygen reduction reaction (ORR) activities. We have developed iron complexes containing N2- or N3-chelating coordination structures with preorganized aromatic rings in a 1,12-diazatriphenylene framework tethering bromo substituents as precursors to precisely construct Fe−N₄ sites in an Fe/N/C catalyst. One-step pyrolysis of the iron complex with carbon black forms atomically dispersed Fe−N₄ sites without iron aggregates. X-ray absorption spectroscopy (XAS) and electrochemical measurements revealed that the iron complex with N3-coordination is more effectively converted to Fe−N₄ sites catalyzing ORR with a TOF value of 0.21 e site⁻¹ s⁻¹ at 0.8 V vs. RHE. This indicates that the formation of Fe−N₄ sites is controlled by precise tuning of the chemical structure of the iron complex precursor.     

Synthesis of Anisotropic Hydrogels and Their Applications

Owing to their water‐rich structures, which are similar to those of biological tissues, hydrogels have long been regarded as promising scaffolds for artificial tissues and organs. However, in terms of the structural anisotropy, most synthetic hydrogels are substantially different from biological systems. Synthetic hydrogels are usually composed of randomly oriented three‐dimensional polymer networks whereas biological systems adopt anisotropic structures with hierarchically integrated building units. Such anisotropic structures often play essential roles in biological systems to exhibit particular functions. In this context, anisotropic hydrogels provide an entry point for exploring biomimetic applications of hydrogels. Reflecting these aspects, an increasing number of studies on anisotropic hydrogels have been reported recently. This Minireview highlights the use and perspectives of these anisotropic hydrogels, particularly focusing on their preparation, structures, and applications.     

New Oxyhalide Solid Electrolytes with High Lithium Ionic Conductivity >10 mS cm−1 for All-Solid-State Batteries

All-solid-state batteries (ASSBs) with inorganic solid electrolytes (SEs) have attracted significant interest as next-generation energy storage. Halides such as Li₃YCl₆ are promising candidates for SE because they combine high oxidation stability and deformability. However, the ionic conductivities of halide SEs are not as high as those of other SEs, especially sulfides. Here, we discover new lithium-metal-oxy-halide materials, LiMOCl₄ (M=Nb, Ta). They exhibit extremely high ionic conductivities of 10.4 mS cm⁻¹ for M=Nb and 12.4 mS cm⁻¹ for M=Ta, respectively, even in cold-pressed powder forms at room temperature, which are comparable to or surpass those of organic liquid electrolytes used in lithium-ion batteries. Bulk-type ASSB cells using the oxyhalides as the cathode SE demonstrate an outstanding rate capability with a capacity retention of 80 % at 5 C/0.1 C. We believe that the proposed oxyhalides are promising SE candidates for the practical applications of ASSBs.     

Selective probe of the morphology and local vibrations at carbon nanoasperities

We introduce a way to selectively probe local vibration modes at nanostructured asperities such as tips of carbon nanohorns. Our observations benefit from signal amplification in surface-enhanced Raman scattering (SERS) at sites near a silver surface. We observe nanohorn tip vibration modes in the range 200-500 cm(-1), which are obscured in regular Raman spectra. Ab initio density functional calculations assign modes in this frequency range to local vibrations at the nanohorn cap resembling the radial breathing mode of fullerenes. Careful interpretation of our SERS spectra indicates presence of caps with 5 or 6 pentagons, which are chemically the most active sites. Changes in the peak intensities and frequencies with time indicate that exposure to laser irradiation may cause structural rearrangements at the cap.