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Single-Electron Lanthanide-Lanthanide Bonds Inside Fullerenes toward Robust Redox-Active Molecular Magnets
A characteristic phenomenon of lanthanide-fullerene interactions is the transfer of metal valence electrons to the carbon cage. With early lanthanides such as La, a complete transfer of six valence electrons takes place for the metal dimers encapsulated in the fullerene cage. However, the low energy of the σ-type Ln-Ln bonding orbital in the second half of the lanthanide row limits the Ln2 → fullerene transfer to only five electrons. One electron remains in the Ln-Ln bonding orbital, whereas the fullerene cage with a formal charge of -5 is left electron-deficient. Such Ln2@C80 molecules are unstable in the neutral form but can be stabilized by substitution of one carbon atom by nitrogen to give azafullerenes Ln2@C79N or by quenching the unpaired electron on the fullerene cage by reacting it with a chemical such as benzyl bromide, transforming one sp2 carbon into an sp3 carbon and yielding the monoadduct Ln2@C80(CH2Ph). Because of the presence of the Ln-Ln bonding molecular orbital with one electron, the Ln2@C79N and Ln2@C80(R) molecules feature a unique single-electron Ln-Ln bond and an unconventional +2.5 oxidation state of the lanthanides.In this Account, which brings together metallofullerenes, molecular magnets, and lanthanides in unconventional valence states, we review the progress in the studies of dimetallofullerenes with single-electron Ln-Ln bonds and highlight the consequences of the unpaired electron residing in the Ln-Ln bonding orbital for the magnetic interactions between Ln ions. Usually, Ln···Ln exchange coupling in polynuclear lanthanide compounds is weak because of the core nature of 4f electrons. However, when interactions between Ln centers are mediated by a radical bridge, stronger coupling may be achieved because of the diffuse nature of radical-based orbitals. Ultimately, when the role of a radical bridge is played by a single unpaired electron in the Ln-Ln bonding orbital, the strength of the exchange coupling is increased dramatically. Giant exchange coupling in endohedral Ln2 dimers is combined with a rather strong axial ligand field exerted on the lanthanide ions by the fullerene cage and the excess electron density localized between two Ln ions. As a result, Ln2@C79N and Ln2@C80(CH2Ph) compounds exhibit slow relaxation of magnetization and exceptionally high blocking temperatures for Ln = Dy and Tb. At low temperatures, the [Ln3+-e-Ln3+] fragment behaves as a single giant spin. Furthermore, the Ln-Ln bonding orbital in dimetallofullerenes is redox-active, which allows its population to be changed by electrochemical reactions, thus changing the magnetic properties because the change in the number of electrons residing in the Ln-Ln orbital affects the magnetic structure of the molecule. © 2019 American Chemical Society.
High-quality MgB2 nanocrystals synthesized by using modified amorphous nano-boron powders: Study of defect structures and superconductivity properties
Nano sized magnesium diboride (MgB2) samples were synthesized using various high-quality nano-B precursor powders. The microscopic defect structures of MgB2 samples were systematically investigated using X-ray powder diffraction, Raman, resistivity measurements and electron paramagnetic resonance spectroscopy. A significant deviation in the critical temperature Tc was observed due to defects and crystal distortion. The symmetry effect of the latter is also reflected on the vibrational modes in the Raman spectra. Scanning electron microscopy analysis demonstrate uniform and ultrafine morphology for the modified MgB2. Defect center in particular Mg vacancies influence the connectivity and the conductivity properties which are crucial for the superconductivity applications.
Optimal principal component analysis of stem xeds spectrum images
STEM XEDS spectrum images can be drastically denoised by application of the principal component analysis (PCA). This paper looks inside the PCA workflow step by step on an example of a complex semiconductor structure consisting of a number of different phases. Typical problems distorting the principal components decomposition are highlighted and solutions for the successful PCA are described. Particular attention is paid to the optimal truncation of principal components in the course of reconstructing denoised data. A novel accurate and robust method, which overperforms the existing truncation methods is suggested for the first time and described in details.
Ultrahigh Power Factor in Thermoelectric System Nb0.95M0.05FeSb (M = Hf, Zr, and Ti)
Conversion efficiency and output power are crucial parameters for thermoelectric power generation that highly rely on figure of merit ZT and power factor (PF), respectively. Therefore, the synergistic optimization of electrical and thermal properties is imperative instead of optimizing just ZT by thermal conductivity reduction or just PF by electron transport enhancement. Here, it is demonstrated that Nb0.95Hf0.05FeSb has not only ultrahigh PF over ≈100 µW cm−1 K−2 at room temperature but also the highest ZT in a material system Nb0.95M0.05FeSb (M = Hf, Zr, Ti). It is found that Hf dopant is capable to simultaneously supply carriers for mobility optimization and introduce atomic disorder for reducing lattice thermal conductivity. As a result, Nb0.95Hf0.05FeSb distinguishes itself from other outstanding NbFeSb-based materials in both the PF and ZT. Additionally, a large output power density of ≈21.6 W cm−2 is achieved based on a single-leg device under a temperature difference of ≈560 K, showing the realistic prospect of the ultrahigh PF for power generation.
Structural and mechanical characterization of heterogeneities in a CuZr-based bulk metallic glass processed by high pressure torsion
Cu45Zr45Al5Ag5 bulk metallic glass samples, processed by high pressure torsion (HPT) under various conditions, were characterized using synchrotron X-ray diffraction, nanoindentation, differential scanning calorimetry, atomic force and transmission electron microscopy. The experimental results clearly show that HPT modifies the amorphous structure by increasing the mean atomic volume. The level of rejuvenation, correlated with the excess mean atomic volume, is enhanced at higher shear strains as inferred from relaxation enthalpies. By mapping of structural and mechanical quantities, the strain-induced rejuvenated state is characterized on cross-sectional HPT samples on a local scale. A clear correlation both between elastic and plastic softening and between softening and excess mean atomic volume is obtained. But also the heterogeneity of the HPT induced rejuvenation is revealed, resulting in the formation of highly strain-softened regions next to less-deformed ones. A hardness drop of up to 20% is associated with an estimated increase of the mean atomic volume of up to 0.75%. Based on synchrotron X-ray diffraction and nanoindentation measurements it is concluded that elastic fluctuations are enhanced in the rejuvenated material on different length scales down to atomic scale. Furthermore, the calculated flexibility volume and the corresponding average mean square atomic displacement is increased. The plastic response during nanoindentation indicates that HPT processing promotes a more homogeneous-like deformation.
Self-Assembled Flexible and Integratable 3D Microtubular Asymmetric Supercapacitors
The rapid development of microelectronics has equally rapidly increased the demand for miniaturized energy storage devices. On-chip microsupercapacitors (MSCs), as promising power candidates, possess great potential to complement or replace electrolytic capacitors and microbatteries in various applications. However, the areal capacities and energy densities of the planar MSCs are commonly limited by the low voltage window, the thin layer of the electrode materials and complex fabrication processes. Here, a new-type three-dimensional (3D) tubular asymmetric MSC with small footprint area, high potential window, ultrahigh areal energy density, and long-term cycling stability is fabricated with shapeable materials and photolithographic technologies, which are compatible with modern microelectronic fabrication procedures widely used in industry. Benefiting from the novel architecture, the 3D asymmetric MSC displays an ultrahigh areal capacitance of 88.6 mF cm−2 and areal energy density of 28.69 mW h cm−2, superior to most reported interdigitated MSCs. Furthermore, the 3D tubular MSCs demonstrate remarkable cycling stability and the capacitance retention is up to 91.8% over 12 000 cycles. It is believed that the efficient fabrication methodology can be used to construct various integratable microscale tubular energy storage devices with small footprint area and high performance for miniaturized electronics.
The influence of the in-plane lattice constant on the superconducting transition temperature of FeSe0.7Te0.3 thin films
Epitaxial Fe(Se,Te) thin films were prepared by pulsed laser deposition on (La0.18Sr0.82)(Al0.59Ta0.41)O3 (LSAT), CaF2-buffered LSAT and bare CaF2 substrates, which exhibit an almost identical in-plane lattice parameter. The composition of all Fe(Se,Te) films were determined to be FeSe0.7Te0.3 by energy dispersive X-ray spectroscopy, irrespective of the substrate. Albeit the lattice parameters of all templates have comparable values, the in-plane lattice parameter of the FeSe0.7Te0.3 films varies significantly. We found that the superconducting transition temperature (Tc) of FeSe0.7Te0.3 thin films is strongly correlated with their a-axis lattice parameter. The highest Tc of over 19 K was observed for the film on bare CaF2 substrate, which is related to unexpectedly large in-plane compressive strain originating mostly from the thermal expansion mismatch between the FeSe0.7Te0.3 film and the substrate.
High Blocking Temperature of Magnetization and Giant Coercivity in the Azafullerene Tb 2 @C 79 N with a Single-Electron Terbium–Terbium Bond
The azafullerene Tb 2 @C 79 N is found to be a single-molecule magnet with a high 100-s blocking temperature of magnetization of 24 K and large coercivity. Tb magnetic moments with an easy-axis single-ion magnetic anisotropy are strongly coupled by the unpaired spin of the single-electron Tb−Tb bond. Relaxation of magnetization in Tb 2 @C 79 N below 15 K proceeds via quantum tunneling of magnetization with the characteristic time τ QTM =16 462±1230 s. At higher temperature, relaxation follows the Orbach mechanism with a barrier of 757±4 K, corresponding to the excited states, in which one of the Tb spins is flipped. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
Single Molecule Magnetism with Strong Magnetic Anisotropy and Enhanced Dy∙∙∙Dy Coupling in Three Isomers of Dy-Oxide Clusterfullerene Dy2O@C82
A new class of single-molecule magnets (SMMs) based on Dy-oxide clusterfullerenes is synthesized. Three isomers of Dy2O@C82 with Cs(6), C3v(8), and C2v(9) cage symmetries are characterized by single-crystal X-ray diffraction, which shows that the endohedral Dy−(µ2-O)−Dy cluster has bent shape with very short Dy−O bonds. Dy2O@C82 isomers show SMM behavior with broad magnetic hysteresis, but the temperature and magnetization relaxation depend strongly on the fullerene cage. The short Dy−O distances and the large negative charge of the oxide ion in Dy2O@C82 result in the very strong magnetic anisotropy of Dy ions. Their magnetic moments are aligned along the Dy−O bonds and are antiferromagnetically (AFM) coupled. At low temperatures, relaxation of magnetization in Dy2O@C82 proceeds via the ferromagnetically (FM)-coupled excited state, giving Arrhenius behavior with the effective barriers equal to the AFM-FM energy difference. The AFM-FM energy differences of 5.4–12.9 cm−1 in Dy2O@C82 are considerably larger than in SMMs with {Dy2O2} bridges, and the Dy∙∙∙Dy exchange coupling in Dy2O@C82 is the strongest among all dinuclear Dy SMMs with diamagnetic bridges. Dy-oxide clusterfullerenes provide a playground for the further tuning of molecular magnetism via variation of the size and shape of the fullerene cage.
Electrically-Pumped Wavelength-Tunable GaAs Quantum Dots Interfaced with Rubidium Atoms
We demonstrate the first wavelength-tunable electrically pumped source of nonclassical light that can emit photons with wavelength in resonance with the D2 transitions of 87Rb atoms. The device is fabricated by integrating a novel GaAs single-quantum-dot light-emitting diode (LED) onto a piezoelectric actuator. By feeding the emitted photons into a 75 mm long cell containing warm 87Rb vapor, we observe slow-light with a temporal delay of up to 3.4 ns. In view of the possibility of using 87Rb atomic vapors as quantum memories, this work makes an important step toward the realization of hybrid-quantum systems for future quantum networks.