12 results
Search Results
Now showing 1 - 10 of 12
- ItemEngineering Kitaev exchange in stacked iridate layers: Impact of inter-layer species on in-plane magnetism(Cambridge : Royal Society of Chemistry, 2019) Yadav, R.; Eldeeb, M.S.; Ray, R.; Aswartham, S.; Sturza, M.I.; Nishimoto, S.; Van Den Brink, J.; Hozoi, L.Novel functionalities may be achieved in oxide electronics by appropriate stacking of planar oxide layers of different metallic species, MOp and M′Oq. The simplest mechanism allowing the tailoring of the electronic states and physical properties of such heterostructures is of electrostatic nature - charge imbalance between the M and M′ cations. Here we clarify the effect of interlayer electrostatics on the anisotropic Kitaev exchange in H3LiIr2O6, a recently proposed realization of the Kitaev spin liquid. By quantum chemical calculations, we show that the precise position of H+ cations between magnetically active [LiIr2O6]3- honeycomb-like layers has a strong impact on the magnitude of Kitaev interactions. In particular, it is found that stacking with straight interlayer O-H-O links is detrimental to in-plane Kitaev exchange since coordination by a single H-ion of the O ligand implies an axial Coulomb potential at the O site and unfavorable polarization of the O 2p orbitals mediating the Ir-Ir interactions. Our results therefore provide valuable guidelines for the rational design of Kitaev quantum magnets, indicating unprecedented Kitaev interactions of ≈40 meV if the linear interlayer linkage is removed.
- ItemStabilizing a three-center single-electron metal–metal bond in a fullerene cage(Cambridge : RSC, 2021) Jin, Fei; Xin, Jinpeng; Guan, Runnan; Xie, Xiao-Ming; Chen, Muqing; Zhang, Qianyan; Popov, Alexey A.; Xie, Su-Yuan; Yang, ShangfengTrimetallic carbide clusterfullerenes (TCCFs) encapsulating a quinary M3C2 cluster represent a special family of endohedral fullerenes with an open-shell electronic configuration. Herein, a novel TCCF based on a medium-sized rare earth metal, dysprosium (Dy), is synthesized for the first time. The molecular structure of Dy3C2@Ih(7)-C80 determined by single crystal X-ray diffraction shows that the encapsulated Dy3C2 cluster adopts a bat ray configuration, in which the acetylide unit C2 is elevated above the Dy3 plane by ∼1.66 Å, while Dy–Dy distances are ∼3.4 Å. DFT computational analysis of the electronic structure reveals that the endohedral cluster has an unusual formal charge distribution of (Dy3)8+(C2)2−@C806− and features an unprecedented three-center single-electron Dy–Dy–Dy bond, which has never been reported for lanthanide compounds. Moreover, this electronic structure is different from that of the analogous Sc3C2@Ih(7)-C80 with a (Sc3)9+(C2)3−@C806− charge distribution and no metal–metal bonding.
- ItemExpansion of the (BB)Ru metallacycle with coinage metal cations: Formation of B-M-Ru-B (M = Cu, Ag, Au) dimetalacyclodiboryls(Cambridge : Royal Society of Chemistry, 2018) Eleazer, B.J.; Smith, M.D.; Popov, A.A.; Peryshkov, D.V.In this work, we introduce a novel approach for the selective assembly of heterometallic complexes by unprecedented coordination of coinage metal cations to strained single ruthenium-boron bonds on a surface of icosahedral boron clusters. M(i) cations (M = Cu, Ag, and Au) insert into B-Ru bonds of the (BB)-carboryne complex of ruthenium with the formation of four-membered B-M-Ru-B metalacycles. Results of theoretical calculations suggest that bonding within these metalacycles can be best described as unusual three-center-two-electron B-M⋯Ru interactions that are isolobal to B-H⋯Ru borane coordination for M = Cu and Ag, or the pairs of two-center-two electron B-Au and Au-Ru interactions for M = Au. These transformations comprise the first synthetic route to exohedral coinage metal boryl complexes of icosahedral closo-{C2B10} clusters, which feature short Cu-B (2.029(2) Å) and Ag-B (2.182(3) Å) bonds and the shortest Au-B bond (2.027(2) Å) reported to date. The reported heterometallic complexes contain Cu(i) and Au(i) centers in uncharacteristic square-planar coordination environments. These findings pave the way to rational construction of a broader class of multimetallic architectures featuring M-B bonds.
- ItemHigh temperature behavior of rual thin films on piezoelectric CTGS and LGS substrates(Basel : MDPI AG, 2020) Seifert, M.This paper reports on a significant further improvement of the high temperature stability of RuAl thin films (110 nm) on the piezoelectric Ca3TaGa3Si2O14 (CTGS) and La3Ga5SiO14 (LGS) substrates. RuAl thin films with AlN or SiO2 cover layers and barriers to the substrate (each 20 nm), as well as a combination of both were prepared on thermally oxidized Si substrates, which serve as a reference for fundamental studies, and the piezoelectric CTGS, as well as LGS substrates. In somefilms, additional Al layers were added. To study their high temperature stability, the samples were annealed in air and in high vacuum up to 900 °C, and subsequently their cross-sections, phase formation, film chemistry, and electrical resistivity were analyzed. It was shown that on thermally oxidized Si substrates, all films were stable after annealing in air up to 800 °C and in high vacuum up to 900 °C. The high temperature stability of RuAl thin films on CTGS substrates was improved up to 900 °C in high vacuum by the application of a combined AlN/SiO2 barrier layer and up to 800 °C in air using a SiO2 barrier. On LGS, the films were only stable up to 600 °C in air; however, a single SiO2 barrier layer was sufficient to prevent oxidation during annealing at 900 °C in high vacuum.
- ItemPhase formation and high-temperature stability of very thin co-sputtered Ti-Al and multilayered Ti/Al films on thermally oxidized si substrates(Basel : MDPI AG, 2020) Seifert, M.; Lattner, E.; Menzel, S.B.; Oswald, S.; Gemming, T.Ti-Al thin films with a thickness of 200 nm were prepared either by co-sputtering from elemental Ti and Al targets or as Ti/Al multilayers with 10 and 20 nm individual layer thickness on thermally oxidized Si substrates. Some of the films were covered with a 20-nm-thick SiO2 layer, which was used as an oxidation protection against the ambient atmosphere. The films were annealed at up to 800 °C in high vacuum for 10 h, and the phase formation as well as the film architecture was analyzed by X-ray diffraction, cross section, and transmission electron microscopy, as well as Auger electron and X-ray photoelectron spectroscopy. The results reveal that the co-sputtered films remained amorphous after annealing at 600 °C independent on the presence of the SiO2 cover layer. In contrast to this, the γ-TiAl phase was formed in the multilayer films at this temperature. After annealing at 800 °C, all films were degraded completely despite the presence of the cover layer. In addition, a strong chemical reaction between the Ti and SiO2 of the cover layer and the substrate took place, resulting in the formation of Ti silicide. In the multilayer samples, this reaction already started at 600 °C.
- ItemTiNb2O7 and VNB9O25 of ReO3 type in hybrid Mg−Li batteries: Electrochemical and interfacial insights(Washington, DC : American Chemical Society, 2020) Maletti, Sebastian; Herzog-Arbeitman, Abraham; Oswald, Steffen; Senyshyn, Anatoliy; Giebeler, Lars; Mikhailova, DariaAs one of the beyond-lithium battery concepts, hybrid metal-ion batteries have aroused growing interest. Here, TiNb2O7 (TNO) and VNb9O25 (VNO) materials were prepared using a high-temperature solid-state synthesis and, for the first time, comprehensively examined in hybrid Mg−Li batteries. Both materials adopt ReO3-related structures differing in the interconnection of oxygen polyhedra and the resulting guest ion diffusion paths. We show applicability of the compounds in hybrid cells providing capacities comparable to those reached in Li-ion batteries (LIBs) at room temperature (220 mAh g−1 for TNO and 150 mAh g−1 for VNO, both at 0.1 C), their operability in the temperature range between −10 and 60 °C, and even better capacity retention than in pure LIBs, rendering this hybrid technology superior for long-term application. Post mortem X-ray photoelectron spectroscopy reveals a cathode−electrolyte interface as a key ingredient for providing excellent electrochemical stability of the hybrid battery. A significant contribution of the intercalation pseudocapacitance to charge storage was observed for both materials in Li- and Mg−Li batteries. However, the pseudocapacitive part is higher for TNO than for VNO, which correlates with structural distinctions, providing better accessibility of diffusion pathways for guest cations in TNO and, as a consequence, a higher ionic transport within the crystal structure. © 2020 American Chemical Society
- ItemStabilization of the ζ-Cu10Sn3 Phase by Ni at Soldering-Relevant Temperatures(Heidelberg : Springer Verlag, 2020) Wieser, C.; Hügel, W.; Martin, S.; Freudenberger, J.; Leineweber, A.A current issue in electrical engineering is the enhancement of the quality of solder joints. This is mainly associated with the ongoing electrification of transportation as well as the miniaturization of (power) electronics. For the reliability of solder joints, intermetallic phases in the microstructure of the solder are of great importance. The formation of the intermetallic phases in the Cu-Sn solder system was investigated for different annealing temperatures between 472 K and 623 K using pure Cu as well as Cu-1at.%Ni and Cu-3at.%Ni substrate materials. These are relevant for lead frame materials in electronic components. The Cu and Cu-Ni alloys were in contact to galvanic plated Sn. This work is focused on the unexpected formation of the hexagonal ζ-(Cu,Ni)10Sn3 phase at annealing temperatures of 523–623 K, which is far below the eutectoid decomposition temperature of binary ζ-Cu10Sn3 of about 855 K. By using scanning electron microscopy, energy dispersive X-ray spectroscopy, electron backscatter diffraction and X-ray diffraction the presence of the ζ phase was confirmed and its structural properties were analyzed.
- ItemThe electronic structure of ϵ-Ga2O3(Melville, NY : AIP Publ., 2019) Mulazzi, M.; Reichmann, F.; Becker, A.; Klesse, W.M.; Alippi, P.; Fiorentini, V.; Parisini, A.; Bosi, M.; Fornari, R.The electronic structure of ε-Ga2O3 thin films has been investigated by ab initio calculations and photoemission spectroscopy with UV, soft, and hard X-rays to probe the surface and bulk properties. The latter measurements reveal a peculiar satellite structure in the Ga 2p core level spectrum, absent at the surface, and a core-level broadening that can be attributed to photoelectron recoil. The photoemission experiments indicate that the energy separation between the valence band and the Fermi level is about 4.4 eV, a valence band maximum at the Γ point and an effective mass of the highest lying bands of – 4.2 free electron masses. The value of the bandgap compares well with that obtained by optical experiments and with that obtained by calculations performed using a hybrid density-functional, which also reproduce well the dispersion and density of states.
- ItemSingle-crystalline FeCo nanoparticle-filled carbon nanotubes: Synthesis, structural characterization and magnetic properties(Frankfurt am Main : Beilstein-Institut zur Förderung der Chemischen Wissenschaften, 2018) Ghunaim, R.; Scholz, M.; Damm, C.; Rellinghaus, B.; Klingeler, R.; Büchner, B.; Mertig, M.; Hampel, S.In the present work, we demonstrate different synthesis procedures for filling carbon nanotubes (CNTs) with equimolar binary nanoparticles of the type Fe-Co. The CNTs act as templates for the encapsulation of magnetic nanoparticles and provide a protective shield against oxidation as well as prevent nanoparticle agglomeration. By variation of the reaction parameters, we were able to tailor the sample purity, degree of filling, the composition and size of the filling particles, and therefore, the magnetic properties. The samples were analyzed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), superconducting quantum interference device (SQUID) and thermogravimetric analysis (TGA). The Fe-Co-filled CNTs show significant enhancement in the coercive field as compared to the corresponding bulk material, which make them excellent candidates for several applications such as magnetic storage devices.
- ItemSpin-glass state and reversed magnetic anisotropy induced by Cr doping in the Kitaev magnet α-RuCl3(College Park, MD : American Physical Society, 2019) Bastien, G.; Roslova, M.; Haghighi, M.H.; Mehlawat, K.; Hunger, J.; Isaeva, A.; Doert, T.; Vojta, M.; Büchner, B.; Wolter, A.U.B.Magnetic properties of the substitution series Ru1-xCrxCl3 were investigated to determine the evolution from the anisotropic Kitaev magnet α-RuCl3 with Jeff=1/2 magnetic Ru3+ ions to the isotropic Heisenberg magnet CrCl3 with S=3/2 magnetic Cr3+ ions. Magnetization measurements on single crystals revealed a reversal of the magnetic anisotropy under doping, which we argue to arise from the competition between anisotropic Kitaev and off-diagonal interactions on the Ru-Ru links and approximately isotropic Cr-Ru and isotropic Cr-Cr interactions. In addition, combined magnetization, ac susceptibility, and specific-heat measurements clearly show the destabilization of the long-range magnetic order of α-RuCl3 in favor of a spin-glass state of Ru1-xCrxCl3 for a low doping of x≤0.1. The corresponding freezing temperature as a function of Cr content shows a broad maximum around x ≤ 0.45.