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- ItemAmorphous-Like Ultralow Thermal Transport in Crystalline Argyrodite Cu7PS6(Weinheim : Wiley-VCH, 2024) Shen, Xingchen; Ouyang, Niuchang; Huang, Yuling; Tung, Yung‐Hsiang; Yang, Chun‐Chuen; Faizan, Muhammad; Perez, Nicolas; He, Ran; Sotnikov, Andrei; Willa, Kristin; Wang, Chen; Chen, Yue; Guilmeau, EmmanuelDue to their amorphous-like ultralow lattice thermal conductivity both below and above the superionic phase transition, crystalline Cu- and Ag-based superionic argyrodites have garnered widespread attention as promising thermoelectric materials. However, despite their intriguing properties, quantifying their lattice thermal conductivities and a comprehensive understanding of the microscopic dynamics that drive these extraordinary properties are still lacking. Here, an integrated experimental and theoretical approach is adopted to reveal the presence of Cu-dominated low-energy optical phonons in the Cu-based argyrodite Cu7PS6. These phonons yield strong acoustic-optical phonon scattering through avoided crossing, enabling ultralow lattice thermal conductivity. The Unified Theory of thermal transport is employed to analyze heat conduction and successfully reproduce the experimental amorphous-like ultralow lattice thermal conductivities, ranging from 0.43 to 0.58 W m−1 K−1, in the temperature range of 100–400 K. The study reveals that the amorphous-like ultralow thermal conductivity of Cu7PS6 stems from a significantly dominant wave-like conduction mechanism. Moreover, the simulations elucidate the wave-like thermal transport mainly results from the contribution of Cu-associated low-energy overlapping optical phonons. This study highlights the crucial role of low-energy and overlapping optical modes in facilitating amorphous-like ultralow thermal transport, providing a thorough understanding of the underlying complex dynamics of argyrodites.
- ItemFloating Zone Growth of Pure and Pb-Doped Bi-2201 Crystals(Basel : MDPI, 2024) Roslova, Maria; Büchner, Bernd; Maljuk, AndreyIn this review, we summarize recent progress in crystal growth and understanding of the influence of crystal structure on superconductivity in pure and Pb-doped Bi2Sr2CuOy (Bi-2201) materials belonging to the overdoped region of high-temperature cuprate superconductors. The crystal growth of Bi-2201 superconductors faces challenges due to intricate materials chemistry and the lack of knowledge of corresponding phase diagrams. Historically, a crucible-free floating zone method emerged as the most promising growth approach for these materials, resulting in high-quality single crystals. This review outlines the described methods in the literature and the authors’ synthesis endeavors encompassing Pb-doped Bi-2201 crystals, provides a detailed structural characterization of as-grown and post-growth annealed samples, and highlights optimal growth conditions that yield large-size, single-phase, and compositionally homogeneous Bi-2201 single crystals.
- ItemThe Weak 3D Topological Insulator Bi12Rh3Sn3I9(Weinheim : Wiley-VCH, 2020) Lê Anh, Mai; Kaiser, Martin; Ghimire, Madhav Prasad; Richter, Manuel; Koepernik, Klaus; Gruschwitz, Markus; Tegenkamp, Christoph; Doert, Thomas; Ruck, MichaelTopological insulators (TIs) gained high interest due to their protected electronic surface states that allow dissipation-free electron and information transport. In consequence, TIs are recommended as materials for spintronics and quantum computing. Yet, the number of well-characterized TIs is rather limited. To contribute to this field of research, we focused on new bismuth-based subiodides and recently succeeded in synthesizing a new compound Bi12Rh3Sn3I9, which is structurally closely related to Bi14Rh3I9 – a stable, layered material. In fact, Bi14Rh3I9 is the first experimentally supported weak 3D TI. Both structures are composed of well-defined intermetallic layers of ∞2[(Bi4Rh)3I]2+ with topologically protected electronic edge-states. The fundamental difference between Bi14Rh3I9 and Bi12Rh3Sn3I9 lies in the composition and the arrangement of the anionic spacer. While the intermetallic 2D TI layers in Bi14Rh3I9 are isolated by ∞1[Bi2I8]2− chains, the isoelectronic substitution of bismuth(III) with tin(II) leads to ∞2[Sn3I8]2− layers as anionic spacers. First transport experiments support the 2D character of this material class and revealed metallic conductivity. © 2020 The Authors. Published by Wiley-VCH GmbH
- ItemAnharmonic strong-coupling effects at the origin of the charge density wave in CsV3Sb5([London] : Nature Publishing Group UK, 2024) He, Ge; Peis, Leander; Cuddy, Emma Frances; Zhao, Zhen; Li, Dong; Zhang, Yuhang; Stumberger, Romona; Moritz, Brian; Yang, Haitao; Gao, Hongjun; Devereaux, Thomas Peter; Hackl, RudiThe formation of charge density waves is a long-standing open problem, particularly in dimensions higher than one. Various observations in the vanadium antimonides discovered recently further underpin this notion. Here, we study the Kagome metal CsV3Sb5 using polarized inelastic light scattering and density functional theory calculations. We observe a significant gap anisotropy with 2Δmax/kBTCDW≈20, far beyond the prediction of mean-field theory. The analysis of the A1g and E2g phonons, including those emerging below TCDW, indicates strong phonon-phonon coupling, presumably mediated by a strong electron-phonon interaction. Similarly, the asymmetric Fano-type lineshape of the A1g amplitude mode suggests strong electron-phonon coupling below TCDW. The large electronic gap, the enhanced anharmonic phonon-phonon coupling, and the Fano shape of the amplitude mode combined are more supportive of a strong-coupling phonon-driven charge density wave transition than of a Fermi surface instability or an exotic mechanism in CsV3Sb5.
- ItemTuning the interplay between nematicity and spin fluctuations in Na1-x Li x FeAs superconductors(London : Nature Publishing Group, 2018) Baek, S.-H.; Bhoi, D.; Nam, W.; Lee, B.; Efremov, D.V.; Büchner, B.; Kim, K.H.Strong interplay of spin and charge/orbital degrees of freedom is the fundamental characteristic of the iron-based superconductors (FeSCs), which leads to the emergence of a nematic state as a rule in the vicinity of the antiferromagnetic state. Despite intense debate for many years, however, whether nematicity is driven by spin or orbital fluctuations remains unsettled. Here, by use of transport, magnetization, and 75As nuclear magnetic resonance (NMR) measurements, we show a striking transformation of the relationship between nematicity and spin fluctuations (SFs) in Na1-x Li x FeAs; For x ≤ 0.02, the nematic transition promotes SFs. In contrast, for x ≥ 0.03, the system undergoes a non-magnetic phase transition at a temperature T 0 into a distinct nematic state that suppresses SFs. Such a drastic change of the spin fluctuation spectrum associated with nematicity by small doping is highly unusual, and provides insights into the origin and nature of nematicity in FeSCs.
- ItemGiant thermal expansion and α-precipitation pathways in Ti-Alloys(London : Nature Publishing Group, 2017) Bönisch, M.; Panigrahi, A.; Stoica, M.; Calin, M.; Ahrens, E.; Zehetbauer, M.; Skrotzki, W.; Eckert, J.Ti-Alloys represent the principal structural materials in both aerospace development and metallic biomaterials. Key to optimizing their mechanical and functional behaviour is in-depth know-how of their phases and the complex interplay of diffusive vs. displacive phase transformations to permit the tailoring of intricate microstructures across a wide spectrum of configurations. Here, we report on structural changes and phase transformations of Ti-Nb alloys during heating by in situ synchrotron diffraction. These materials exhibit anisotropic thermal expansion yielding some of the largest linear expansion coefficients (+ 163.9×10-6 to-95.1×10-6 °C-1) ever reported. Moreover, we describe two pathways leading to the precipitation of the α-phase mediated by diffusion-based orthorhombic structures, α″lean and α″iso. Via coupling the lattice parameters to composition both phases evolve into α through rejection of Nb. These findings have the potential to promote new microstructural design approaches for Ti-Nb alloys and β-stabilized Ti-Alloys in general.
- ItemA diuranium carbide cluster stabilized inside a C80 fullerene cage(London : Nature Publishing Group, 2018) Zhang, X.; Li, W.; Feng, L.; Chen, X.; Hansen, A.; Grimme, S.; Fortier, S.; Sergentu, D.-C.; Duignan, T.J.; Autschbach, J.; Wang, S.; Wang, Y.; Velkos, G.; Popov, A.A.; Aghdassi, N.; Duhm, S.; Li, X.; Li, J.; Echegoyen, L.; Schwarz, W.H.E.; Chen, N.Unsupported non-bridged uranium-carbon double bonds have long been sought after in actinide chemistry as fundamental synthetic targets in the study of actinide-ligand multiple bonding. Here we report that, utilizing I h(7)-C80 fullerenes as nanocontainers, a diuranium carbide cluster, U=C=U, has been encapsulated and stabilized in the form of UCU@I h(7)-C80. This endohedral fullerene was prepared utilizing the Krätschmer-Huffman arc discharge method, and was then co-crystallized with nickel(II) octaethylporphyrin (NiII-OEP) to produce UCU@I h(7)-C80·[NiII-OEP] as single crystals. X-ray diffraction analysis reveals a cage-stabilized, carbide-bridged, bent UCU cluster with unexpectedly short uranium-carbon distances (2.03 Å) indicative of covalent U=C double-bond character. The quantum-chemical results suggest that both U atoms in the UCU unit have formal oxidation state of +5. The structural features of UCU@I h(7)-C80 and the covalent nature of the U(f1)=C double bonds were further affirmed through various spectroscopic and theoretical analyses.
- ItemCollapse of layer dimerization in the photo-induced hidden state of 1T-TaS2([London] : Nature Publishing Group UK, 2020) Stahl, Quirin; Kusch, Maximilian; Heinsch, Florian; Garbarino, Gaston; Kretzschmar, Norman; Hanff, Kerstin; Rossnagel, Kai; Geck, Jochen; Ritschel, TobiasPhoto-induced switching between collective quantum states of matter is a fascinating rising field with exciting opportunities for novel technologies. Presently, very intensively studied examples in this regard are nanometer-thick single crystals of the layered material 1T-TaS2, where picosecond laser pulses can trigger a fully reversible insulator-to-metal transition (IMT). This IMT is believed to be connected to the switching between metastable collective quantum states, but the microscopic nature of this so-called hidden quantum state remained largely elusive up to now. Here, we characterize the hidden quantum state of 1T-TaS2 by means of state-of-the-art x-ray diffraction and show that the laser-driven IMT involves a marked rearrangement of the charge and orbital order in the direction perpendicular to the TaS2-layers. More specifically, we identify the collapse of interlayer molecular orbital dimers as a key mechanism for this non-thermal collective transition between two truly long-range ordered electronic crystals.
- ItemSingle molecule magnet with an unpaired electron trapped between two lanthanide ions inside a fullerene(London : Nature Publishing Group, 2017) Liu, F.; Krylov, D.S.; Spree, L.; Avdoshenko, S.M.; Samoylova, N.A.; Rosenkranz, M.; Kostanyan, A.; Greber, T.; Wolter, A.U.B.; Büchner, B.; Popov, A.A.Increasing the temperature at which molecules behave as single-molecule magnets is a serious challenge in molecular magnetism. One of the ways to address this problem is to create the molecules with strongly coupled lanthanide ions. In this work, endohedral metallofullerenes Y 2 @C 80 and Dy 2 @C 80 are obtained in the form of air-stable benzyl monoadducts. Both feature an unpaired electron trapped between metal ions, thus forming a single-electron metal-metal bond. Giant exchange interactions between lanthanide ions and the unpaired electron result in single-molecule magnetism of Dy 2 @C 80 (CH 2 Ph) with a record-high 100 s blocking temperature of 18 K. All magnetic moments in Dy 2 @C 80 (CH 2 Ph) are parallel and couple ferromagnetically to form a single spin unit of 21 μ B with a dysprosium-electron exchange constant of 32 cm -1. The barrier of the magnetization reversal of 613 K is assigned to the state in which the spin of one Dy centre is flipped.
- ItemSyntheses and Molecular Structures of Liquid Pyrophoric Hydridosilanes(Weinheim : Wiley-VCH, 2020) Gerwig, Maik; Böhme, Uwe; Friebel, Mike; Gründler, Franziska; Franze, Georg; Rosenkranz, Marco; Schmidt, Horst; Kroke, EdwinTrisilane, isotetrasilane, neopentasilane, and cyclohexasilane have been prepared in gram scale. In-situ cryo crystallization of these pyrophoric liquids in sealed capillaries on the diffractometer allows access to the single crystal structures of these compounds. Structural parameters are discussed and compared to gas-phase electron diffraction structures from literature and with the results from quantum chemical calculations. Significantly higher packing indices are found for the silanes compared to the corresponding alkanes. Radiation with ultraviolet light (365 nm) and parallel ESR (EPR) measurement shows that cyclohexasilane is easily split into radicals, which subsequently leads to the formation of branched and chain-like oligomers. The other compounds form no radicals under these conditions. NMR spectra of all four compounds have been recorded. © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.