Search

Transition metal phosphide alloying is an effective approach for optimizing the electronic structure and improving the intrinsic performance of the hydrogen evolution reaction (HER). However, obtaining 3d transition metal phosphides alloyed with noble metals is still a challenge owing to their difference in electronegativity, and the influence of their electronic structure modulated by noble metals on the HER reaction also remains unclear. In this study, we successfully incorporated Ru into an Fe

The classification scheme of electronic phases uses two prominent paradigms: correlations and topology. Electron correlations give rise to superconductivity and charge density waves, while the quantum geometric Berry phase gives rise to electronic topology. The intersection of these two paradigms has initiated an effort to discover electronic instabilities at or near the Fermi level of topological materials. Here we identify the electronic topology of chiral fermions as the driving mechanism for creating van Hove singularities that host electronic instabilities in the surface band structure. We observe that the chiral fermion conductors RhSi and CoSi possess two types of helicoid arc van Hove singularities that we call type I and type II. In RhSi, the type I variety drives a switching of the connectivity of the helicoid arcs at different energies. In CoSi, we measure a type II intra-helicoid arc van Hove singularity near the Fermi level. Chemical engineering methods are able to tune the energy of these singularities. Finally, electronic susceptibility calculations allow us to visualize the dominant Fermi surface nesting vectors of the helicoid arc singularities, consistent with recent observations of surface charge density wave ordering in CoSi. This suggests a connection between helicoid arc singularities and surface charge density waves. Nanyang Technological University National Research Foundation (NRF) Submitted/Accepted version Work at Princeton University and Princeton-led synchrotron based ARPES measurements were supported by the U.S. Department of Energy (DOE) under the Basic Energy Sciences programme (grant no. DOE/BES DE-FG-02-05ER46200). This research used resources of the Advanced Light Source, which is a DOE Office of Science User Facility under contract No. DE-AC02-05CH11231. We acknowledge the Paul Scherrer Institut, Villigen, Switzerland for provision of synchrotron radiation beam time at the ADRESS beam line of the Swiss Light Source. G.C. acknowledges support from the National Research Foundation, Singapore under NRF fellowship award no. NRF-NRFF13-2021-0010 and a Nanyang Assistant Professorship grant from Nanyang Technological University. K.M. acknowledges the Department of Atomic Energy (DAE), Government of India for funding support via a young scientist’s research award (YSRA) with grant no. 58/20/03/2021-BRNS/37084. T.A.C. was supported by the National Science Foundation Graduate Research Fellowship Program under grant no. DGE-1656466.

In a joint effort utilizing modified sample preparation, microscopy, X‐ray diffraction and micro‐fabrication, it became possible to prepare single crystals of the “hidden” phase AlCr2. High‐resolution X‐ray diffraction analysis is described in detail for two crystals with the similar overall composition, but different degree of disorder, which seems to be the main cause for the differing unit cell parameters. Chemical bonding analysis of AlCr2 in comparison to prototypical MoSi2 shows pronounced differences reflecting the interchange of main group element vs. transition metal as majority component., Hidden crystals: With a modified synthesis approach and micro‐fabrication technique, it was possible to isolate micrometer‐sized single crystals of AlCr2 from a largely polycrystalline sample. Chemical bond analysis shows close relation to elements, in contrast to a quite localized bonding pattern in the prototype, MoSi2.

The clathrate-I borosilicide K8−xBySi46−y (0.8 ≤ x ≤ 1.2 and 6.4 ≤ y ≤ 7.2; space group Pmn) was prepared in sealed tantalum ampoules between 900 °C and 1000 °C. By high-pressure preparation at 8 GPa and 1000 °C, a higher boron content is achieved (x = 0.2, y = 7.8). Crystal structure and composition were established from X-ray diffraction data, chemical analysis, WDX spectroscopy, and confirmed by 11B and 29Si NMR, and magnetic susceptibility measurements. The compositions are electron-balanced according to the Zintl rule within one estimated standard deviation. The lattice parameter varies with composition from a = 9.905 A for K7.85(2)B7.8(1)Si38.2(1) to a = 9.968(1) A for K6.80(2)B6.4(5)Si39.6(5).

The topological Hall effect (THE), induced by the Berry curvature that originates from non-zero scalar spin chirality, is an important feature for mesoscopic topological structures, such as skyrmions. However, the THE might also arise from other microscopic non-coplanar spin structures in the lattice. Thus, the origin of the THE inevitably needs to be determined to fully understand skyrmions and find new host materials. Here, we examine the Hall effect in both, bulk- and micron-sized lamellar samples of MnBi. The sample size affects the temperature and field range in which the THE is detectable. Although a bulk sample exhibits the THE only upon exposure to weak fields in the easy-cone state, in micron-sized lamella the THE exists across a wide temperature range and occurs at fields near saturation. Our results show that both the non-coplanar spin structure in the lattice and topologically non-trivial skyrmion bubbles are responsible for the THE, and that the dominant mechanism depends on the sample size. Hence, the magnetic phase diagram for MnBi is size-dependent. Our study provides an example in which the THE is simultaneously induced by two mechanisms, and builds a bridge between mesoscopic and microscopic magnetic structures. © 2022. This work was financially supported by an Advanced Grant from the European Research Council (No. 742068 ) “TOPMAT,” the European Union's Horizon 2020 research and innovation programme (No. 824123 ) “SKYTOP,” the European Union's Horizon 2020 research and innovation programme (No. 766566 ) “ASPIN,” the Deutsche Forschungsgemeinschaft (Project-ID 258499086) “SFB 1143,” the Deutsche Forschungsgemeinschaft (Project-IDs FE 633/30-1, RE 1164/6-1 and LU 2261/2-1) “SPP Skyrmionics,” the DFG through the Würzburg-Dresden Cluster of Excellence on Complexity and Topology in Quantum Matter ct.qmat (EXC 2147, Project-ID 39085490). I.S. is grateful to Deutsche Forschungsgemeinschaft for supporting this work through project SO 1623/2-1. D.W. has received funding from the European Research Council (ERC) under the Horizon 2020 research and innovation program of the European Union (grant agreement number 715620 ).

Magnetic topological insulators provide an important platform for realizing several exotic quantum phenomena, such as the axion insulating state and the quantum anomalous Hall effect, owing to the interplay between topology and magnetism. MnBi4Te7 is a two-dimensional Z(2) antiferromagnetic (AFM) topological insulator with a Ne ' el temperature of similar to 13 K. In AFM materials, the topological Hall effect (THE) is observed owing to the existence of nontrivial spin structures. A material with noncollinearity that develops in the AFM phase rather than at the onset of the AFM order is particularly important. In this study, we observed that such an unanticipated THE starts to develop in a MnBi4Te7 single crystal when the magnetic field is rotated away from the easy axis (c-axis) of the system. Furthermore, the THE resistivity reaches a giant value of similar to 7 mu Omega-cm at 2 K when the angle between the magnetic field and the c-axis is 75 degrees. This value is significantly higher than the values for previously reported systems with noncoplanar structures. The THE can be ascribed to the noncoplanar spin structure resulting from the canted state during the spinflip transition in the ground AFM state of MnBi4Te7. The large THE at a relatively low applied field makes the MnBi4Te7 system a potential candidate for spintronic applications.

Magnetic topological insulators provide an important platform for realizing several exotic quantum phenomena, such as the axion insulating state and the quantum anomalous Hall effect, owing to the interplay between topology and magnetism. MnBi4Te7 is a two-dimensional Z2 antiferromagnetic (AFM) topological insulator with a Néel temperature of ∼13 K. In AFM materials, the topological Hall effect (THE) is observed owing to the existence of nontrivial spin structures. A material with noncollinearity that develops in the AFM phase rather than at the onset of the AFM order is particularly important. In this study, we observed that such an unanticipated THE starts to develop in a MnBi4Te7 single crystal when the magnetic field is rotated away from the easy axis (c-axis) of the system. Furthermore, the THE resistivity reaches a giant value of ∼7 μΩ-cm at 2 K when the angle between the magnetic field and the c-axis is 75°. This value is significantly higher than the values for previously reported systems with noncoplanar structures. The THE can be ascribed to the noncoplanar spin structure resulting from the canted state during the spin-flip transition in the ground AFM state of MnBi4Te7. The large THE at a relatively low applied field makes the MnBi4Te7 system a potential candidate for spintronic applications.

In this study, faceted mesocrystals have been assembled from the dispersion of truncated cubic-shaped iron oxide nanoparticles stabilized by oleic acid (OA) molecules using the non-solvent “gas phase diffusion technique” into an organic solvent. The effects of synthesis conditions as well as of the nanoparticle size and shape on the structure and morphogenesis of mesocrystals were examined. The interactions of OA capped iron oxide nanoparticles with solvent molecules were probed by analytical ultracentrifugation and double difference pair distribution function analysis. It was shown that the structure of the organic shell significantly depends on the nature and polarity of solvent molecules.

In this study, faceted mesocrystals have been assembled from the dispersion of truncated cubic-shaped iron oxide nanoparticles stabilized by oleic acid (OA) molecules using the non-solvent “gas phase diffusion technique” into an organic solvent. The effects of synthesis conditions as well as of the nanoparticle size and shape on the structure and morphogenesis of mesocrystals were examined. The interactions of OA capped iron oxide nanoparticles with solvent molecules were probed by analytical ultracentrifugation and double difference pair distribution function analysis. It was shown that the structure of the organic shell significantly depends on the nature and polarity of solvent molecules.

The crystal structure of the (Cr,Ni)4Si phase with and without Co was refined from X-ray powder diffraction data. The compound crystallises with an Au4Al-type structure (Pearson symbol cP20, space group P213): unit-cell parameter a = 0.611959(6) nm for the composition (Cr0.312Ni0.688)4Si, a = 0.612094(6) nm for (Cr0.375Ni0.625)4Si, and a = 0.612316(6) nm for (Cr0.337Co0.063Ni0.600)4Si. The magnetic susceptibility was measured in external fields up to 7 T at temperatures between 1.8 and 400 K. The three investigated samples exhibited paramagnetic behaviour described by the modified Curie-Weiss law: χ0 = 146∙10-6 emu g-at.-1, μeff = 0.21 μB/atom, θP = -13 K for (Cr0.312Ni0.688)4Si; χ0 = 158∙10-6 emu g-at.-1, μeff = 0.20 μB/atom, θP = -15 K for (Cr0.375Ni0.625)4Si; χ0 = 169∙10-6 emu g-at.-1, μeff = 0.18 μB/atom, θP = -52 K for (Cr0.337Co0.063Ni0.600)4Si.

The discovery of high thermoelectric performance in n-type polycrystalline Mg3(Sb,Bi)2 based Zintl compounds has ignited intensive research interest. However, some fundamental questions concerning the anisotropic transport properties and the origin of intrinsically low thermal conductivity are still elusive, requiring the investigation of single crystals. In this work, high-quality p-type Mg3Sb2 and Mg3Bi2 single crystals have been grown by using a self-flux method. The electrical resistivity \r{ho} of Mg3Bi2 single crystal displays an anisotropy with \r{ho} in-plane twice larger than out-of-plane. The low-temperature heat capacity and lattice thermal conductivity of Mg3Sb2 and Mg3Bi2 single crystals have been investigated by using the Debye-Callaway model, from which the existence of low-lying vibration mode could be concluded. Large Gr\"uneisen parameters and strong anharmonicity are found responsible for the intrinsically low thermal conductivity. Moreover, grain boundary scattering does not contribute significantly to suppress the lattice thermal conductivity of polycrystalline Mg3Sb2. Our results provide insights into the intrinsic transport properties of Mg3X2 and could pave a way to realize enhanced thermoelectric performance in single-crystalline Mg3X2-based Zintl compounds.

We investigate flux-grown Sm-deficient Sm$_x$B$_6$ ($x < 1$) by global and local tools, including X-ray diffraction (XRD), electronic transport, and scanning tunneling microscopy (STM) and spectroscopy (STS). All these tools indicate a remarkable persistence of the SmB$_6$ local structure in the flux-grown samples even for nominal Sm concentrations as low as $x=0.75$. As a consequence, the overall electronic properties of Sm$_x$B$_6$, and particularly the surface conductance at low temperature, is only affected locally by the Sm-deficiency., 9 pages, 8 figures

As conductors in electronic applications shrink, microscopic conduction processes lead to strong deviations from Ohm's law. Depending on the length scales of momentum conserving ($l_{MC}$) and relaxing ($l_{MR}$) electron scattering, and the device size ($d$), current flows may shift from ohmic to ballistic to hydrodynamic regimes and more exotic mixtures thereof. So far, an in situ, in-operando methodology to obtain these parameters self-consistently within a micro/nanodevice, and thereby identify its conduction regime, is critically lacking. In this context, we exploit Sondheimer oscillations, semi-classical magnetoresistance oscillations due to helical electronic motion, as a method to obtain $l_{MR}$ in micro-devices even when $l_{MR}\gg d$. This gives information on the bulk $l_{MR}$ complementary to quantum oscillations, which are sensitive to all scattering processes. We extract $l_{MR}$ from the Sondheimer amplitude in the topological semi-metal WP$_2$, at elevated temperatures up to $T\sim 50$~K, in a range most relevant for hydrodynamic transport phenomena. Our data on micrometer-sized devices are in excellent agreement with experimental reports of the large bulk $l_{MR}$ and thus confirm that WP$_2$ can be microfabricated without degradation. Indeed, the measured scattering rates match well with those of theoretically predicted electron-phonon scattering, thus supporting the notion of strong momentum exchange between electrons and phonons in WP$_2$ at these temperatures. These results conclusively establish Sondheimer oscillations as a quantitative probe of $l_{MR}$ in micro-devices in studying non-ohmic electron flow., 14 pages with 4 figures

The clathrate-I borosilicide K

Despite the fundamental nature of the edge state in topological physics, direct measurement of electronic and optical properties of the Fermi arcs of topological semimetals has posed a significant experimental challenge, as their response is often overwhelmed by the metallic bulk. However, laser-driven currents carried by surface and bulk states can propagate in different directions in nonsymmorphic crystals, allowing for the two components to be easily separated. Motivated by a recent theoretical prediction \cite{chang20}, we have measured the linear and circular photogalvanic effect currents deriving from the Fermi arcs of the nonsymmorphic, chiral Weyl semimetal RhSi over the $0.45 - 1.1$ eV incident photon energy range. Our data are in good agreement with the predicted magnitude of the circular photogalvanic effect as a function of photon energy, although the direction of the surface photocurrent departed from the theoretical expectation over the energy range studied. Surface currents arising from the linear photogalvanic effect were observed as well, with the unexpected result that only two of the six allowed tensor element were required to describe the measurements, suggesting an approximate emergent mirror symmetry inconsistent with the space group of the crystal., Comment: 6+5 pages, 5+3 figures

Physical review / X 11(1), 011002 (2021). doi:10.1103/PhysRevX.11.011002, Herein we show that nonresonant inelastic x-ray scattering involving an $s$ core level is a powerful spectroscopic method to characterize the excited states of transition metal compounds. The spherical charge distribution of the $s$ core hole allows the orientational dependence of the intensities of the various spectral features to produce a spatial charge image of the associated multiplet states in a straightforward manner, thereby facilitating the identification of their orbital character. In addition, the $s$ core hole does not add an extra orbital angular momentum component to the multiplet structure so that the well-established Sugano-Tanabe-Kamimura diagrams can be used for the analysis of the spectra. For $\alpha$-MnS we observe the spherical charge density corresponding to its high-spin $3d^5$ ($^6A_1$) ground state configuration and we were able to selectively image its excited states and identify them as $t_{2g}$ ($^5T_2$) and $e_g$ ($^5E$) with an energy splitting $10Dq$ of 0.78 eV., Published by APS, College Park, Md.

Weyl semimetals (WSMs) hosting Weyl points (WPs) with different chiralities attract great interest as an object to study chirality-related physical properties, topological phase transitions, and topological superconductivity. Quantum oscillation measurements and theoretical calculations imply that the type-II WPs in NbIrTe4 are robust against the shift of chemical potential making it a good material for pressure studies on topological properties. Here we report the results of electrical transport property measurements and Raman spectroscopy studies under pressures up to 65.5 GPa accompanied by theoretical electronic structure calculations. Hall resistivity data reveal an electronic transition indicated by a change of the charge carrier from multiband character to hole-type at ~12 GPa, in agreement with the calculated Fermi surface. An onset of superconducting transition is observed at pressures above 39 GPa, with critical temperature increasing as pressure increases. Moreover, theoretical calculations indicate that WPs persist up to highly reduced unit cell volume (−17%), manifesting that NbIrTe4 is a candidate of topological superconductor.

The emerging class of topological materials provides a platform to engineer exotic electronic structures for a variety of applications. As complex band structures and Fermi surfaces can directly benefit thermoelectric performance it is important to identify the role of featured topological bands in thermoelectrics particularly when there are coexisting classic regular bands. In this work, the contribution of Dirac bands to thermoelectric performance and their ability to concurrently achieve large thermopower and low resistivity in novel semimetals is investigated. By examining the YbMnSb2 nodal line semimetal as an example, the Dirac bands appear to provide a low resistivity along the direction in which they are highly dispersive. Moreover, because of the regular-band-provided density of states, a large Seebeck coefficient over 160 µV K−1 at 300 K is achieved in both directions, which is very high for a semimetal with high carrier concentration. The combined highly dispersive Dirac and regular bands lead to ten times increase in power factor, reaching a value of 2.1 mW m−1 K−2 at 300 K. The present work highlights the potential of such novel semimetals for unusual electronic transport properties and guides strategies towards high thermoelectric performance. © 2020 The Authors. Advanced Materials published by Wiley-VCH GmbH

Enantiomorph-distribution maps for chiral element and multicomponent structures by Electron Backscatter Diffraction., The assignment of enantiomorphs by diffraction methods shows fundamental differences for x-rays and electrons. This is particularly evident for the chiral allotrope of β-Mn. While it is not possible to determine the sense of chirality of β-Mn with established x-ray diffraction methods, Kikuchi pattern simulation of the enantiomorphs reveals differences, if dynamical electron diffraction is considered. Quantitative comparison between experimental and simulated Kikuchi patterns allows the spatially resolved assignment of the enantiomorph in polycrystalline materials of β-Mn, as well as the structurally strongly related phase Pt2Cu3B. On the basis of enantiomorph distribution maps, crystals were extracted from enantiopure domains by micropreparation techniques. The x-ray diffraction analyses confirm the assignment of the Kikuchi pattern evaluations for Pt2Cu3B and do not allow to distinguish between the enantiomorphs of β-Mn.

It has recently been proposed that combining chirality with topological band theory results in a totally new class of fermions. Understanding how these unconventional quasiparticles propagate and interact remains largely unexplored so far. Here, we use scanning tunneling microscopy to visualize the electronic properties of the prototypical chiral topological semimetal PdGa. We reveal chiral quantum interference patterns of opposite spiraling directions for the two PdGa enantiomers, a direct manifestation of the change of sign of their Chern number. Additionally, we demonstrate that PdGa remains topologically non-trivial over a large energy range, experimentally detecting Fermi arcs in an energy window of more than 1.6 eV that is symmetrically centered around the Fermi level. These results are a consequence of the deep connection between chirality in real and reciprocal space in this class of materials, and, thereby, establish PdGa as an ideal topological chiral semimetal., Nature Communications, 11 (1), ISSN:2041-1723

The CPGE spectrum and optical conductivity in RhSi are measured and discussed, comparing to theoretical predictions., Weyl semimetals are crystals in which electron bands cross at isolated points in momentum space. Associated with each crossing point (or Weyl node) is a topological invariant known as the Berry monopole charge. The circular photogalvanic effect (CPGE), whereby circular polarized light generates a helicity-dependent photocurrent, is a notable example of a macroscopic property that emerges directly from the topology of the Weyl semimetal band structure. Recently, it was predicted that the amplitude of the CPGE associated with optical transitions near a Weyl node is proportional to its monopole charge. In chiral Weyl systems, nodes of opposite charge are nondegenerate, opening a window of wavelengths where the CPGE resulting from uncompensated Berry charge can emerge. Here, we report measurements of CPGE in the chiral Weyl semimetal RhSi, revealing a CPGE response in an energy window that closes at 0.65 eV, in agreement with the predictions of density functional theory.

The emerging class of topological materials provides a platform to engineer exotic electronic structures for a variety of applications. As complex band structures and Fermi surfaces can directly benefit thermoelectric performance it is important to identify the role of featured topological bands in thermoelectrics particularly when there are coexisting classic regular bands. In this work, the contribution of Dirac bands to thermoelectric performance and their ability to concurrently achieve large thermopower and low resistivity in novel semimetals is investigated. By examining the YbMnSb

The absence of centrosymmetry in chiral and polar crystal structures is the reason for many technical relevant physical properties like optical birefringence or ferroelectricity. Other chirality related properties that are actually intensively investigated are unconventional superconductivity or unusual magnetic ordering like skyrmions in materials with B20 structure. Despite the often close crystal structure - property relation, its detection is often challenging due to superposition of domains with different absolute structure e.g. chirality. Our investigations of high quality CoSi crystals with B20 structure by both complementary methods X- ray (volume sensitive) and electron backscatter diffraction (EBSD) (surface sensitive) results the consistent assignment of the chirality and reveal fundamental differences in their sensitivity to chirality. The analysis of the surface of a CoSi crystal with domains of different chirality show the high spatial resolution of this method which opens the possibility to analyze the chirality in microstructures of technical relevant materials like thin films and catalysts.

The delafossite metals PdCoO2, PtCoO2, and PdCrO2 are among the highest conductivity materials known, with low-temperature mean free paths of tens of microns in the best as-grown single crystals. A key question is whether these very low resistive scattering rates result from strongly suppressed backscattering due to special features of the electronic structure or are a consequence of highly unusual levels of crystalline perfection. We report the results of experiments in which high-energy electron irradiation was used to introduce point disorder to the Pd and Pt layers in which the conduction occurs. We obtain the cross section for formation of Frenkel pairs in absolute units, and cross-check our analysis with first-principles calculations of the relevant atomic displacement energies. We observe an increase of resistivity that is linear in defect density with a slope consistent with scattering in the unitary limit. Our results enable us to deduce that the as-grown crystals contain extremely low levels of in-plane defects of approximately 0.001%. This confirms that crystalline perfection is the most important factor in realizing the long mean free paths and highlights how unusual these delafossite metals are in comparison with the vast majority of other multicomponent oxides and alloys. We discuss the implications of our findings for future materials research.

The half-Heusler rare-earth intermetallic GdPtBi has recently gained attention due to peculiar magnetotransport phenomena that have been associated with the possible existence of Weyl fermions, thought to arise from the crossings of spin-split conduction and valence bands. On the other hand, similar magnetotransport phenomena observed in other rare-earth intermetallics have often been attributed to the interaction of itinerant carriers with localized magnetic moments stemming from the $4f$-shell of the rare-earth element. In order to address the origin of the magnetotransport phenomena in GdPtBi, we performed a comprehensive study of the magnetization, electrical and thermal magnetoresistivity on two single-crystalline GdPtBi samples. In addition, we performed an analysis of the Fermi surface via Shubnikov-de Haas oscillations in one of the samples and compared the results to \emph{ab initio} band structure calculations. Our findings indicate that the electrical and thermal magnetotransport in GdPtBi cannot be solely explained by Weyl physics and is strongly influenced by the interaction of both itinerant charge carriers and phonons with localized magnetic Gd-ions and possibly also paramagnetic impurities., Comment: 11 figures

The development of high‐density magnetic recording media is limited by superparamagnetism in very small ferromagnetic crystals. Hard magnetic materials with strong perpendicular anisotropy offer stability and high recording density. To overcome the difficulty of writing media with a large coercivity, heat‐assisted magnetic recording was developed, rapidly heating the media to the Curie temperature Tc before writing, followed by rapid cooling. Requirements are a suitable Tc, coupled with anisotropic thermal conductivity and hard magnetic properties. Here, Rh2CoSb is introduced as a new hard magnet with potential for thin‐film magnetic recording. A magnetocrystalline anisotropy of 3.6 MJ m-3 is combined with a saturation magnetization of μ0>7sub>Ms = 0.52 T at 2 K (2.2 MJ m-3 and 0.44 T at room temperature). The magnetic hardness parameter of 3.7 at room temperature is the highest observed for any rare‐earth‐free hard magnet. The anisotropy is related to an unquenched orbital moment of 0.42 μB on Co, which is hybridized with neighboring Rh atoms with a large spin–orbit interaction. Moreover, the pronounced temperature dependence of the anisotropy that follows from its Tc of 450 K, together with a thermal conductivity of 20 W m-1 K-1, make Rh2CoSb a candidate for the development of heat‐assisted writing with a recording density in excess of 10 Tb in.-2.

The crystal structure of the complex intermetallic phase o-Al13Co4 was first investigated in 1994, but some open questions still remained. The new refinement of the crystal structure using high-resolution X-ray diffraction data resulted in a much more complex model including a large number of split positions (space group Pnm21, a = 8.1590(6) Å, b = 12.349(1) Å, c = 14.453(1) Å). The model is interpreted in terms of local violation of the translational symmetry, which is confirmed by HRTEM and HRSTEM investigations. Chemical bonding between two partial structures in o-Al13Co4 - three-dimensional framework and linear Co–Al–Co groups in cages of the latter – along with the stacking faults (local twinning) are discussed as possible reasons for such an extended disorder. Previous article in issue

As a quite unique case a high-temperature modification was previously described for the well-known MoSi2. A detailed reinvestigation, however, proves that even minute amounts of beryllium trigger the formation of a hexagonal CrSi2-type phase rather than the established tetragonal prototype. This ternary MoSi2−xBex is stable at ambient conditions and very likely resembles the high-temperature polymorph of MoSi2. With the help of powder X-ray diffraction, electron backscatter diffraction and energy-dispersive X-ray spectroscopy analyses it was concluded that beryllium replaces silicon atoms in the crystal structure, and that the Be/Si network may contain vacancies.

Two new calcium nitridomanganates, Ca12 [Mn19 N23 ] (P3, a=11.81341(3) A, c=5.58975(2) A, Z=1) and Ca133 [Mn216 N260 ] (P3‾ , a=39.477(1) A, c=5.5974(2) A, Z=1), were obtained by a gas-solid reaction of Ca3 N2 and Mn with N2 at 1273 K and 1223 K, respectively. The crystal structure of Ca12 [Mn19 N23 ] was determined from high-resolution X-ray synchrotron powder diffraction data, whereas single-crystal X-ray diffraction was employed to establish the crystal structure of the Ca133 [Mn216 N260 ] phase, which classifies as a complex metallic alloy (CMA). Both crystal structures have 2D nitridomanganate layers containing similar building blocks but of different levels of structural complexity. Bonding analysis as well as magnetic susceptibility and electron spin resonance measurements revealed that only a fraction of the Mn atoms in both structures carries a localized magnetic moment, while for most Mn species the magnetism is quenched as a result of metal-metal bond formation.

Composites containing biological materials with nanostructured architecture have become of great interest in modern materials science, yielding both interesting chemical properties and inspiration for biomimetic research. Herein, we describe the preparation of a novel 3D nanostructured MnO2-based composite developed using a carbonized proteinaceous spongin template by an extreme biomimetics approach. The thermal stability of the spongin-based scaffold facilitated the formation of both carbonized material (at 650 °C with exclusion of oxygen) and manganese oxide with a defined nanoscale structure under 150 °C. Remarkably, the unique network of spongin fibers was maintained after pyrolysis and hydrothermal processing, yielding a novel porous support. The MnO2-spongin composite shows a bimodal pore distribution, with macropores originating from the spongin network and mesopores from the nanostructured oxidic coating. Interestingly, the composites also showed improved electrochemical properties compared to those of MnO2. Voltammetry cycling demonstrated the good stability of the material over more than 3,000 charging/discharging cycles. Additionally, electrochemical impedance spectroscopy revealed lower charge transfer resistance in the prepared materials. We demonstrate the potential of extreme biomimetics for developing a new generation of nanostructured materials with 3D centimeter-scale architecture for the storage and conversion of energy generated from renewable natural sources.

This study gives an account of an innovative, crucible-free technique for the synthesis of single-phase borides at relatively moderate temperatures. A metal wire heated by an electrical current reacts with a chosen gaseous boron halide in a gas/solid reaction yielding a single-phase, oxygen- and carbon-free product, as evidenced by X-ray powder diffraction and chemical analysis. This method is demonstrated using the example of hafnium reacting with boron tribromide. Preliminary thermodynamic considerations show that this kind of crucible-free synthesis specifically enables the preparation of borides of transition metals and similar elements.

Heusler compounds with heavy elements often display noncollinear magnetic structures, which can lead to phenomena such as the topological Hall effect. In this study, we report the structural, magnetic, electronic, and transport properties of IrMnGa. X-ray and neutron diffraction experiments reveal that the compound crystallizes in the cubic half-Heusler space group 216 with $Y$-type disorder. Manganese occupies two nonequivalent positions, causing frustration and preventing long-range magnetic order. As a consequence, a spin glass state is observed below 74 K. The spin glass state exhibits a pronounced bifurcation between field-cooled and zero-field-cooled magnetization curves, shifted hysteresis loops after field cooling, magnetic relaxation, the memory effect, absence of magnetic-ordering peaks in neutron diffraction, and a sharp cusp of the ac susceptibility. The shift of the freezing temperature as a function of ac frequency is well described by the Vogel-Fulcher law and by a critical-scaling approach indicating that IrMnGa is a canonical spin glass. Magnetotransport (including the anomalous Hall effect) and heat capacity were also investigated.