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233 records · Page 13

Breaking New Ground: MB ene Route toward Selective Vinyl Double Bond Hydrogenation in Nitroarenes

Doping, or incremental substitution of one element for another, is an effective way to tailor a compound’s structure as well as its physical and chemical properties. Herein, we replaced up to 30% of Ni with Co in members of the family of layered LiNiB compounds, stabilizing the high-temperature polymorph of LiNiB while the room-temperature polymorph does not form. By studying this layered boride with in situ high-temperature powder diffraction, we obtained a distorted variant of LiNi 0.7 Co 0.3 B featuring a perfect interlayer placement of [Ni 0.7 Co 0.3 B] layers on top of each other–a structural motif not seen before in other borides. Because of the Co doping, LiNi 0.7 Co 0.3 B can undergo a nearly complete topochemical Li deintercalation under ambient conditions, resulting in a metastable boride with the formula Li 0.04 Ni 0.7 Co 0.3 B. Heating of Li 0.04 Ni 0.7 Co 0.3 B in anaerobic conditions led to yet another metastable boride, Li 0.01 Ni 0.7 Co 0.3 B, with a CoB-type crystal structure that cannot be obtained by simple annealing of Ni, Co, and B. No significant alterations of magnetic properties were detected upon Co-doping in the temperature-independent paramagnet LiNi 0.7 Co 0.3 B or its Li-deintercalated counterparts. Finally, Li 0.01 Ni 0.7 Co 0.3 B stands out as an exceptional catalyst for the selective hydrogenation of the vinyl C=C bond in 3-nitrostyrene, even in the presence of other competing functional groups. Finally, this research showcases an innovative approach to heterogeneous catalyst design by meticulously synthesizing metastable compounds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Quantum Transport in 2D Semiconductors

Leveraging progress in synthesis of ultra-pure transition metal dichalcogenide (TMD) crystals, our team has made key breakthroughs in the study of quantum states in two-dimensional (2D) TMD semiconductors. Using a capacitance spectroscopy technique, we have observed the first signatures of fractional quantum Hall states in monolayer WSe 2 and clear signatures of interlayer exciton condensates in bilayer WSe 2 . In a transport study of bilayer WSe 2 , we report observation of spin-selective magneto-conductivity in WSe 2 . To improve electrical transport studies, we have focused on metal-TMD contacts by studying the behavior of metal-TMD contacts in the clean limit, and developing a new contact doping technique that achieves Ohmic contact down to low temperature and low carrier density. Using this new technique, we study electrical transport in monolayer WSe 2 down to low temperature and low carrier density, finding record-high hole mobility and evidence of a metal-insulator transition at low density. Under high magnetic fields, we observe clear signatures of fractional quantum Hall effect in transport for the first time in a TMD.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Role of the third dimension in searching for Majorana fermions in α-RuCl 3 via phonons

Understanding phonons in α-RuCl 3 is critical to analyze the controversy around the observation of the half-integer thermal quantum Hall effect. While many studies have focused on the magnetic excitations in α-RuCl 3 , its vibrational excitation spectrum has remained relatively unexplored. We investigate the phonon structure of α-RuCl 3 via inelastic neutron-scattering experiments and density-functional-theory calculations. Our results show excellent agreement between experiment and first-principles calculations. After validating our theoretical model, we extrapolate the low-energy phonon properties. We find that the phonons in α-RuCl 3 that either propagate or vibrate in the out-of-plane direction have significantly reduced velocities and therefore have the potential to dominate the observability of the elusive half-integer plateaus in the thermal Hall conductance. In addition, we use low-energy interlayer phonons to resolve the low-temperature stacking structure of our large crystal of α-RuCl 3 , which we find to be consistent with that of the R$\bar{3}$ space group, in agreement with neutron diffraction.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Oscillating paramagnetic Meissner effect and Berezinskii-Kosterlitz-Thouless transition in underdoped Bi2Sr2CaCu2O8+δ

ABSTRACT Superconducting phase transitions in two dimensions lie beyond the description of the Ginzburg-Landau symmetry-breaking paradigm for three-dimensional superconductors. They are Berezinskii-Kosterlitz-Thouless (BKT) transitions of paired-electron condensate driven by the unbinding of topological excitations, i.e. vortices. The recently discovered monolayers of layered high-transition-temperature (${{{T}}}_{{\rm C}}$) cuprate superconductor Bi2Sr2CaCu2O8+δ (Bi2212) meant that this 2D superconductor promised to be ideal for the study of unconventional superconductivity. But inhomogeneity posed challenges for distinguishing BKT physics from charge correlations in this material. Here, we utilize the phase sensitivity of scanning superconducting quantum interference device microscopy susceptometry to image the local magnetic response of underdoped Bi2212 from the monolayer to the bulk throughout its phase transition. The monolayer segregates into domains with independent phases at elevated temperatures below ${{{T}}}_{{\rm C}}$. Within a single domain, we find that the susceptibility oscillates with flux between diamagnetism and paramagnetism in a Fraunhofer-like pattern up to ${{{T}}}_{{\rm C}}$. The finite modulation period, as well as the broadening of the peaks when approaching ${{{T}}}_{{\rm C}}$ from below, suggests well-defined vortices that are increasingly screened by the dissociation of vortex-antivortex plasma through a BKT transition. In the multilayers, the susceptibility oscillation differs in a small temperature regime below ${{{T}}}_{{\rm C}}$, consistent with a dimensional crossover led by interlayer coupling. Serving as strong evidence for BKT transition in the bulk, we observe a sharp jump in phase stiffness and paramagnetism at small fields just below ${{{T}}}_{{\rm C}}$. These results unify the superconducting phase transitions from the monolayer to the bulk underdoped Bi2212, and can be collectively referred to as the BKT transition with interlayer coupling.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Orbital-Dependent Coulomb Drag in Electron-Hole Bilayer Graphene Heterostructures

Here, we report Coulomb drag studies in an electron-hole bilayer graphene heterostructure in a magnetic field, where the orbital, spin, and valley degrees of freedom are lifted by the combined effects of exchange interaction, Zeeman energy, and a vertical displacement field. Our device enables the application of a large vertical displacement field across both layers. In addition to the well-established strong Coulomb drag between the Landau levels with an orbital quantum number 𝑁 = 0, we observe a Coulomb drag signal between the 𝑁 = 1 Landau levels under a suitable vertical displacement field. As the vertical displacement field increases further, the Coulomb drag signal between 𝑁 = 1 Landau levels weakens, and a Coulomb drag signal emerges between the 𝑁 = 0 and 𝑁 = 1 Landau levels. These findings suggest the important roles of the orbital index and the vertical displacement field in interlayer Coulomb interaction within the quantum Hall regime of coupled bilayer systems.

Landau levels↗

Dipole ladders with large Hubbard interaction in a moiré exciton lattice

Two-dimensional semiconductor moiré superlattices have emerged as a powerful platform for engineering correlated electronic phenomena. On the other hand, optical excitation creates charge neutral interlayer excitons with an out-of-plane electric dipole. Strong onsite dipole–dipole interaction promises the formation of correlated bosonic states, akin to the Mott states of electrons, but has not yet been demonstrated. Here we report a large interaction between excitons occupying the same moiré lattice site—characterized by the Hubbard U parameter—and consequent dipole ladders with spin- and electron-filling dependence in WSe 2 /WS 2 moiré superlattices. Photoluminescence measurements show successive peaks emerging with an energy separation of around 34 meV above the ground state as the exciton density is increased. This corresponds to the sequential injection of excitons into a single site with an energy cost to overcome the large exciton Hubbard U, forming a dipole ladder. Based on findings of local magnetic moments at two holes per moiré cell, we show that excitons can also fill a second moiré orbital, establishing the two-orbital nature of the moiré potential landscape. Our results show that the Bose–Hubbard model with possible exciton crystal phases can be investigated in interacting opto-moiré quantum matter.

36 MATERIALS SCIENCE↗

Anomalous thickness-dependent electrical conductivity in van der Waals layered transition metal halide, Nb 3 Cl 8

Understanding the electronic transport properties of layered, van der Waals transition metal halides (TMHs) and chalcogenides is a highly active research topic today. Of particular interest is the evolution of those properties with changing thickness as the 2D limit is approached. Here, we present the electrical conductivity of exfoliated single crystals of the TMH, cluster magnet, Nb 3 Cl 8 , over a wide range of thicknesses both with and without hexagonal boron nitride (hBN) encapsulation. The conductivity is found to increase by more than three orders of magnitude when the thickness is decreased from 280 µm to 5 nm, at 300 K. At low temperatures and below ~50 nm, the conductance becomes thickness independent, implying surface conduction is dominating. Temperature dependent conductivity measurements indicate Nb 3 Cl 8 is an insulator, however, the effective activation energy decreases from a bulk value of 310 meV to 140 meV by 5 nm. X-ray photoelectron spectroscopy (XPS) shows mild surface oxidation in devices without hBN capping, however, no significant difference in transport is observed when compared to the capped devices, implying the thickness dependent transport behavior is intrinsic to the material. A conduction mechanism comprised of a higher conductivity surface channel in parallel with a lower conductivity interlayer channel is discussed.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Pressure and temperature dependences of the canting angle and increase in the magnetic ordering temperature, T c ( P ), for the weak ferromagnet Li + [TCNE]˙ – (TCNE = tetracyanoethylene)

The hydrostatic pressure dependence of the magnetic ordering temperature, T c (P), for the interpenetrating, diamondoid lattice-structured, weak ferromagnet (= canted antiferromagnet) Li + [TCNE]˙ – (TCNE = tetracyanoethylene) reversibly increases from 20.9 to 23.4 K at 9.73 kbar, an increase of 12% with a rate of increase, dT c /dP, of 0.27 K kbar –1 . The 5 T magnetization increased by 672% from 186 emu Oe mol –1 at ambient pressure to an average of 1440 emuOe mol –1 upon application of pressure. The remanent magnetization initially increases 30% from 10.8 to 14.0 emuOe mol –1 from ambient to 0.06 kbar, and increases further by 6% to a maximum of 14.8 emuOe mol –1 at 0.56 kbar before declining by 22% to 11.5 emuOe mol –1 at 9.73 kbar. The pressure-dependent coercive field, H cr (P), initially decreases by 42% from 31.1 Oe at ambient pressure to 18 Oe at 0.06 kbar, then increases to 52 Oe at 9.73 kbar. The canting angle, α, increases by 28% from 0.52° to 0.66° at 0.06 kbar, then decreases by 23% to 0.51° at 9.73 kbar, as well as increases by 2% from 0.536° to 0.548° from 1.8 to 2.5 K, before decreasing by 79% to 0.117° at 19 K. The interlattice interactions are attributed to be the primary exchange mechanism. Furthermore, α(T) and α(P) have similar dependencies that are attributed to a competition between an increase and a decrease in the intra- and interlayer C … N interlattice separations as the temperature and pressure increases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Trigonal symmetry breaking and its electronic effects in the two-dimensional dihalides MX 2 and trihalides MX 3

We study the consequences of the approximately trigonal (D 3d ) point symmetry of the transition metal (M) site in two-dimensional van der Waals MX 2 dihalides and MX 3 trihalides. The trigonal symmetry leads to a 2-2-1 orbital splitting of the transition metal d shell, which is best represented by d orbitals that describe the trigonal rather than Oh symmetry. The ligand-ligand bond length differences (rather than metal-ligand) take the role of a Jahn-Teller-like mode and in combination with interlayer distances and dimensionality effects tune the crystal field splittings and bandwidths. These effects, in turn, are amplified by electronic correlation effects—leading to crystal field splittings of the order of 0.1–1 eV between the singlet and the lowest orbital doublet—as opposed to the often assumed degenerate 3 t 2g states. Our calculations explain why most of the materials in this family are insulating, and why these considerations have to be taken into account in realistic models of them. Further, orbital order coupled to various lower symmetry lattice modes may lift the remaining orbital degeneracies, and we explain how these may support unique electronic states using ZrI 2 and CuCl 2 as examples, and offer a brief overview of possible electronic configurations in this class of materials. By building and analyzing Wannier models adapted to the appropriate symmetry we examine how the interplay among trigonal symmetry, electronic correlation effects, and – d orbital charge transfer leads to insulating, orbitally polarized magnetic and/or orbital-selective Mott states, and we provide a simple framework and numerical tool for others. Our paper establishes a rigorous framework to understand, control, and tune the electronic states in low-dimensional correlated halides. Furthermore, our analysis shows that trigonal symmetry and its breaking is a key feature of the two-dimensional halides that needs to be accounted for in search of novel electronic states in materials ranging from CrI 3 to α–RuCl 3 .

2-dimensional systems↗

Exploring the elastic and electronic properties of chromium molybdenum diboride alloys

We perform first-principles calculations to study the structural, mechanical, thermal, electronic, and magnetic properties of Cr 1-x Mo x B 2 for x = 0.25, 0.33, 0.50, 0.67 and 0.75. Based on structural search methods, we determine the ground-state structure for each concentration. The ternaries are either monoclinic (x = 0.25, 0.75) or trigonal (x = 0.33, 0.50, 0.67). The calculated mechanical properties reveal that the strength of Cr 1-x Mo x B 2 is maximized for x = 0.50. Cr 0.5 Mo 0.5 B 2 exhibits excellent mechanical properties (B = 298 GPa, Y = 558 GPa, G = 235 Gpa, ν = 0.19, H v =27 GPa), surpassing those of β-MoB 2 at a lower cost. All of these ternaries are hard alloys with Vickers hardness greater than 24 GPa. Chemical bonding analysis demonstrates that the strength of the new compounds is related to the alternating planar and buckled B-B layers, as well as the strong TM-B bonds. Finally, the enhanced strength of Cr 0.5 Mo 0.5 B 2 is a consequence of the high density of strong interlayer Cr-Mo metallic bonds around the Fermi level.

36 MATERIALS SCIENCE↗

The Modulated Crystal Structure of K 2 V 3 O 8

Weak lattice distortions can tune exchange pathways and magnetic interactions in square-lattice quantum magnets. K 2 V 3 O 8 is a mixed valence (V 4+ /V 5+ ) fresnoite oxide that exhibits strong spin–lattice coupling at low temperature. Here, we combine single-crystal neutron diffraction (90 K) and laboratory X-ray diffraction (50 K) to solve the low-temperature structure as an orthorhombic (3 + 1)D incommensurately modulated phase in superspace group Cmm2(β,0,1/2)0s0 [No. 196]. What initially appeared as two independent modulation vectors, q 1 = 0.3132(6)[$110$] + 1/2c* and q 2 = 0.3132(6)[$1\bar{10}$] + 1/2c*, are more naturally described as a single one-dimensional modulation wave q = 0.626(1)a* + 1/2c* in a C-centered orthorhombic lattice, related to the parent tetragonal cell by the transformation a + b, −a + b, c. Refinement with a 4-fold rotational twin inherited from the P4bm parent structure solves oxygen-dominated framework distortions and K + displacements. A de Wolff section (t = 0.40) enables a symmetry-mode decomposition, identifying three dominant mm2 (C 2v ) modes: GM3 for framework tilt, A5 for interlayer shear, and Z5 for c-axis breathing. The mode-resolved structure provides a unified, symmetry-based explanation for reported low-temperature Raman and IR anomalies and clarifies the structural origin of the spin–lattice coupling in the S = 1/2 two-dimensional quantum spin compound.

K2V3O8↗

Atomic structure and phase assemblages in novel M-(N)-A-S-H materials

This paper investigates the atomic structure and phase assemblages in new sodium-stabilized magnesium aluminosilicate hydrate (M-(N)-A-S-H) cementitious binders. Results indicate that in the absence of Ca{sup 2+}, Mg{sup 2+} promotes a binder atomic structure of Si-Al tetrahedral sheets and octahedral Mg sheets with hydrated Na{sup +} cations likely in the interlayer sites similar to trioctahedral micas (phyllosilicates). NMR studies verify the incorporation of Al in tetrahedral silicate sheets. XRD demonstrates the ability of these regions to nucleate and form zeolites (i.e., sodalite) as well as the formation of Mg-Al layered double hydroxide (LDH) phases (i.e., meixnerite), which is expected due to high concentrations of Mg and Al. TGA results indicate that M-(N)-A-S-H possesses chemically bound water and hydroxyl units similar to other Mg binders. These results evince the critical role of Mg to form unique atomic structures and durability-linked phases in low-calcium alkali-activated materials.

36 MATERIALS SCIENCE↗

Electronic structure, magnetic correlations, and superconducting pairing in the reduced Ruddlesden-Popper bilayer La 3 Ni 2 O 6 under pressure: Different role of d 3 z 2 - r 2 orbital compared with La 3 Ni 2 O 7

The recent discovery of superconductivity in bilayer La 3 Ni 2 O 7 (327-LNO) under pressure stimulated much interest in layered nickelates. However, superconductivity was not found in another bilayer nickelate system, La 3 Ni 2 O 6 (326-LNO), even under pressure. To understand the similarities and differences between 326-LNO and 327-LNO, using density functional theory and the random phase approximation (RPA), we systematically investigate 326-LNO under pressure. The large crystal-field splitting between the e g orbitals caused by the missing apical oxygen moves the d 3z 2 -r 2 orbital farther away from the Fermi level, implying that the d 3z 2 -r 2 orbital plays a less important role in 326-LNO than in 327-LNO. This also results in a smaller bandwidth for the d x 2 -y 2 orbital and a reduced energy gap for the bonding-antibonding splitting of the d 3z 2 -r 2 orbital in 326-LNO, as compared to 327-LNO. Moreover, the in-plane hybridization between the d x 2 -y 2 and d 3z 2 -r 2 orbitals is found to be small in 326-LNO, while it is much stronger in 327-LNO. Furthermore, the low-spin ferromagnetic state is found to be the likely ground state in 326-LNO under high pressure. The weak interlayer coupling suggests that s ± -wave pairing is unlikely in 326-LNO. The robust in-plane ferromagnetic coupling also suggests that d-wave superconductivity, which is usually caused by antiferromagnetic fluctuations of the d x 2 -y 2 orbital, is also unlikely in 326-LNO. These conclusions are supported by our many-body RPA calculations of the pairing behavior. Additionally, contrasting with the cuprates, for the bilayer cuprate HgBa 2 CaCu 2 O 6 , we find a strong self-doping effect of the d x 2 -y 2 orbital under pressure, with the charge of Cu being reduced by approximately 0.13 electrons from 0 GPa to 25 GPa. In contrast, we do not observe such a change in the electronic density in 326-LNO under pressure, establishing another important difference between the nickelates and the cuprates.

36 MATERIALS SCIENCE↗

Improving charge transport in integrated MoO 3 /C electrode materials for water-in-salt energy storage systems by incorporating oxygen vacancies

Improvements in the charge storage properties of α-MoO 3 used as an electrode with a 30m ZnCl 2 water-in-salt electrolyte have been achieved by enhancements in electron and ion transport enabled by an inventive synthesis route. Electron transport was improved through the integration of MoO 3 with dopamine-derived carbon via a chemical preintercalation route, and enhanced ion transport was achieved by incorporating oxygen vacancies in MoO 3 structure through ethanol 2 reduction under hydrothermal conditions. Here, the presence of carbon was confirmed by corresponding D and G bands observed in Raman spectroscopy measurements. The presence of oxygen vacancies was proven through correlated XPS, TGA, Raman spectroscopy and XRD analyses, with the introduction of oxygen vacancies leading to an expanded interlayer region. Four-point probe measurements provided evidence of increased electronic conductivity due to the incorporation of carbon, and cyclic voltammetry-based charge storage mechanism analyses revealed increases in ion transport kinetics due to oxygen vacancy formation. Tuning the oxygen vacancy concentration is critical, as excessive concentrations of these point defects leads to structural instability and poor capacity retention. This work demonstrates the combined potential of carbon and oxygen vacancies in moderate concentrations to enhance the charge storage properties of transition metal oxides. The strategies developed in this study offer a path to the development of promising materials for high-rate, high-capacity, and long-duration electrochemical energy storage technologies.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

51 V NMR evidence for interlayer-modulated charge order and a first-order low-temperature transition in CsV 3 ⁢Sb 5

Charge order in the kagome superconductor CsV 3 ⁢Sb 5 exhibits a complex three-dimensional organization and intermediate-temperature anomalies whose bulk character has remained unsettled. We use orientation-dependent 51 V NMR as a site-selective probe to determine the stacking of the charge density wave (CDW) state and its thermal evolution. Below 𝑇 CDW ≈ 94K, the field-linear splitting of the 51 V central transition together with the anisotropy of the Knight shift tensor identify an interlayer-modulated 3⁢𝑞 CDW whose local environments are consistent with a four-layer 2 × 2 × 4 stacking with mixed trihexagonal/Star-of-David distortions, in agreement with synchrotron x-ray determinations. For comparison, RbV 3 ⁢Sb 5 serves as a reference exhibiting a uniform trihexagonal 2 × 2 × 2 stacking, allowing us to isolate features unique to the 2 × 2 × 4 state in CsV 3 ⁢Sb 5 . With 𝐻 0 ∥ 𝑐, the 51 V quadrupolar satellites through the intermediate temperature scale near 𝑇 CO ≈ 65K reorganize into two well-resolved electric-field-gradient manifolds that coexist over a finite interval; their relative spectral weights interchange on cooling while the total integrated satellite intensity remains conserved and 𝜈 𝑄 within each manifold is nearly temperature independent. The coexistence without critical broadening, together with conserved intensity, provides bulk evidence consistent with a first-order charge-order transition near 𝑇 CO . Our measurements do not resolve whether this lower-temperature transition corresponds to a distinct in-plane order or a reorganization of the 3⁢𝑞 state; rather, they delimit this window and provide bulk, site-resolved constraints that connect prior reported anomalies to a thermodynamic first-order transition.

Wang, Xiaoling [California State Univ., East Bay, ↗

Quasiparticle spectroscopy in tantalum films with different Ta/sapphire interfaces

One of the crucial aspects of current research in quantum information science is the identification and control of loss mechanisms in superconducting (SC) circuits. Although microwave measurements directly quantify device performance, additional techniques that probe quasiparticle excitations in SC films are needed to understand the microscopic mechanisms underlying dissipation and decoherence. Here, we present results from quasiparticle spectroscopy of Ta/sapphire films by measuring the Meissner-state magnetic susceptibility using a precision frequency-domain resonator specifically designed for thin films. We find direct evidence for additional low-energy excitations in samples with lower internal quality factors. These excitations are consistent with deep subgap states due to two-level systems, Yu–Shiba–Rusinov states near the gap edge, and perhaps other pair-breaking mechanisms. The developed non-destructive frequency-domain quasiparticle spectroscopy is a valuable addition to the quantum materials toolbox.

metal/substrate interlayer↗

Tuning Anisotropic Optical Properties of Inorganic and Hybrid Organic–Inorganic MXenes via Topochemical Surface Modification

Surface groups are central to the properties of MXenes, yet their role in optical anisotropy remains largely unexplored. Here, we use a topochemical route to synthesize single crystals of stacked Ti 3 C 2 Cl 2 and hybrid organic–inorganic MXenes (h-MXenes) with lateral sizes of 38–75 μm, rotational registry, and tunable interlayer spacing. Solid-state NMR spectroscopy shows that topochemical substitution generates mixed amido, imido, and hydride surface motifs, which modify the electronic structure of the Ti 3 C 2 inorganic core. Imaging spectroscopic ellipsometry with micron-scale spatial resolution enables reconstruction of the complex dielectric tensor of individual multilayer crystals. Ti 3 C 2 Cl 2 exhibits a type-II hyperbolicity above 930 nm, whereas h-MXenes do not display hyperbolicity within the measured 300–1700 nm window, instead showing reduced in-plane conductivity, suppressed out-of-plane light absorption, and a chain-length-dependent blue shift of a near-infrared absorption feature. These results demonstrate topochemical surface modification as a direct handle for engineering MXenes as surface-programmable optical media.

Hybrid materials↗