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At least 1,243 records · Page 69

Proximity Spin–Orbit Torque on a Two-Dimensional Magnet within van der Waals Heterostructure: Current-Driven Antiferromagnet-to-Ferromagnet Reversible Nonequilibrium Phase Transition in Bilayer CrI 3

The recently discovered two-dimensional magnetic insulator CrI 3 is an intriguing case for basic research and spintronic applications since it is a ferromagnet in the bulk but an antiferromagnet in bilayer form, with its magnetic ordering amenable to external manipulations. Using the first-principles quantum transport approach, we predict that injecting unpolarized charge current parallel to the interface of the bilayer-CrI 3 /monolayer-TaSe 2 van der Waals (vdW) heterostructure will induce spin–orbit torque and thereby drive the dynamics of magnetization on the first monolayer of CrI 3 in direct contact with TaSe 2 . By combining the calculated complex angular dependence of spin–orbit torque with the Landau-Lifshitz-Gilbert equation for classical dynamics of magnetization, we demonstrate that current pulses can switch the direction of magnetization on the first monolayer to become parallel to that of the second monolayer, thereby converting CrI 3 from antiferromagnet to ferromagnet while not requiring any external magnetic field. We explain the mechanism of this reversible current-driven nonequilibrium phase transition by showing that first monolayer of CrI 3 carries current due to evanescent wave functions injected by metallic transition metal dichalcogenide TaSe 2 , while concurrently acquiring strong spin–orbit coupling via such a proximity effect, whereas the second monolayer of CrI 3 remains insulating. Furthermore, the transition can be detected by passing vertical read current through the vdW heterostructure, encapsulated by a bilayer of hexagonal boron nitride and sandwiched between graphite electrodes, where we find a tunneling magnetoresistance of ≃240%.

2D magnetic materials↗

Vertical Strain-Driven Antiferromagnetic to Ferromagnetic Phase Transition in EuTiO 3 Nanocomposite Thin Films

Three-dimensional (3D) strain induced in self-assembled vertically aligned nanocomposite (VAN) epitaxial films provides an unrivaled method to induce very large strains in thin films. Here, by growing VAN films of EuTiO 3 (ETO)–Eu 2 O 3 (EO) with different EO fractions, the vertical strain was systematically increased in ETO, up to 3.15%, and the Eu–Ti–Eu bond angle along $\langle$111$\rangle$ decreased by up to 1°, leading to a weakening of the antiferromagnetic interactions and switching from antiferromagnetic to ferromagnetic behavior. Our work has shown for the first time that Eu–Ti–Eu superexchange interactions play a key role in determining the magnetic ground state of ETO. Broadly, our work serves as an exemplar to show that multifunctionalities in strong spin–lattice coupling perovskite oxides can be uniquely tuned at the atomic scale using simple VAN structures.

36 MATERIALS SCIENCE↗

Ligand Controls Excited Charge Carrier Dynamics in Metal-Rich CdSe Quantum Dots: Computational Insights

Small metal-rich semiconducting quantum dots (QDs) are promising for solid-state lighting and single-photon emission due to their highly tunable yet narrow emission line widths. Nonetheless, the anionic ligands commonly employed to passivate these QDs exert a substantial influence on the optoelectronic characteristics, primarily owing to strong electron–phonon interactions. In this work, we combine time-domain density functional theory and nonadiabatic molecular dynamics to investigate the excited charge carrier dynamics of Cd 28 Se 17 X 22 QDs (X = HCOO – , OH – , Cl – , and SH – ) at ambient conditions. These chemically distinct but regularly used molecular groups influence the dynamic surface-ligand interfacial interactions in Cd-rich QDs, drastically modifying their vibrational characteristics. The strong electron–phonon coupling leads to substantial transient variations at the band edge states. The strength of these interactions closely depends on the physicochemical characteristics of passivating ligands. Consequently, the ligands largely control the nonradiative recombination rates and emission characteristics in these QDs. Our simulations indicate that Cd 28 Se 17 (OH) 22 has the fastest nonradiative recombination rate due to the strongest electron–phonon interactions. Conversely, QDs passivated with thiolate or chloride exhibit considerably longer carrier lifetimes and suppressed nonradiative processes. The ligand-controlled electron–phonon interactions further give rise to the broadest and narrowest intrinsic optical line widths for OH and Cl-passivated single QDs, respectively. Finally, obtained computational insights lay the groundwork for designing appropriate passivating ligands on metal-rich QDs, making them suitable for a wide range of applications, from blue LEDs to quantum emitters.

36 MATERIALS SCIENCE↗

Excitation Laser Energy Dependence of the Gap-Mode TERS Spectra of WS 2 and MoS 2 on Silver

In this work we present a systematic study of the dependence of the gap mode tip-enhanced Raman scattering (TERS) response of the mono- and bi-layer WS 2 and MoS 2 on silver as a function of the excitation laser energy in a broad spectral range from 473nm to 830 nm. For this purpose, we collected consecutive TERS maps of the same area in the sample containing mono-and bi-layer regions with the same TERS probe with 6 different excitation lasers. To decrease the number of collected TERS maps, we used for the first time to the best of our knowledge, concurrent excitation and collection with two lasers simultaneously. We found that the E 2g /A 1g peak intensity ratio for the bilayer WS 2 @Ag and the ratio of the A’/A 1g peak intensity of the out-of-plane mode for the mono- and the bilayer, change in a significantly non-monotonous way as the excitation laser energy is swept from 1.58 eV to 2.62 eV. The former ratio increases at energies corresponding to A and B excitons (~2.0 eV and 2.4 eV correspondingly) in bilayer WS 2 . The absolute intensity of the A’ peak in the monolayer, and correspondingly the A’/A 1g ratio, is surprisingly high at lower excitation energies, but dips dramatically at the energy corresponding to the A exciton, being restored partially in between A and B excitons, but still showing the descending trend as the excitation laser energy increases. A somewhat similar picture was observed in mono- and bi-layers of MoS 2 @Ag, though the existing set of excitation lasers did not match the excitonic profile of this material as nicely as for the case of WS 2 . We attribute the observed behavior to the presence of intermediate (Fano resonance) or strong (Rabi splitting) coupling between the excitons in transition metal dichalcogenides (TMDs) and the plasmons in the tip-substrate nanocavity. This is akin to the so-called Fano (Rabi) transparency experimentally observed in far field scattering from transition metal dichalcogenides between two plasmonic metals. The possibility of the formation of intermediate/strong coupling between the excitonic resonances in TMDs and the nanocavity re-evaluates the role of various resonances in the gap-mode TERS and should become an important factor to be considered by TERS practitioners during planning the experiments. Lastly, based on observed phenomena and its explanation, we propose the “ideal” substrate for efficient TERS and tip enhanced photoluminescence (TEPL) measurements.

Raman spectroscopy↗

Photoinduced Magnetic Exchange-Jump Promotes Ground State Biradical Electron Spin Polarization

Photoinduced electron spin polarization (ESP) is reported in the electronic ground states of three Pt(II) complexes that are comprised of two S = ½ nitronyl nitroxide (NN) radicals attached through different length para-phenylethynyl bridges to the 3,6 positions of a catecholate (CAT, donor) and 4,4’-di-tert-butyl-2,2’-bipyridine (bpy, acceptor). Complexes 1-3 have from 17 to 41 bonds separating NN radicals, and display cw-EPR spectra consistent with |J NN-NN | >> |a N |, |J NN-NN | ≥ |a N |, and |J NN-NN | < |a N |, respectively, where J NN-NN is the magnetic exchange coupling between NN radicals in the electronic ground state, and a N is the isotropic 14 N hyperfine coupling constant. Light-induced transient EPR spectra characterized as enhanced ground-state absorption were observed for all three complexes using 532 nm pulsed laser excitation into the ligand-to-ligand charge transfer (LL’CT) band of the (CAT)Pt(bpy) chromophore. The magnitude of the observed ESP increases in the order 1 < 2 < 3 and is inversely correlated with the magnitude of ground-state J NN-NN . In addition to the experimental observation net absorptive polarization in 1-3, light excitation also produces multiplet polarization in 2. Since the weak dipolar coupling leads to strong spectral overlap of the absorptive and emissive components, the multiplet polarization is not observed in 1 and 3 and is very weak in 2. Here, the ability to spin polarize multiple radical spins with a single photon is anticipated to advance new photoinduced multi qubit/qudit ESP protocols for quantum information science applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Coercive Fields Exceeding 30 T in the Mixed-Valence Single-Molecule Magnet (Cp iPr5 ) 2 Ho 2 I 3

Mixed-valence dilanthanide complexes of the type (Cp iPr5 ) 2 Ln 2 I 3 (Cp iPr5 = pentaisopropylcyclopentadienyl; Ln = Gd, Tb, Dy) featuring a direct Ln–Ln σ-bonding interaction have been shown to exhibit well-isolated high-spin ground states and, in the case of the Tb and Dy variants, a strong axial magnetic anisotropy that gives rise to a large magnetic coercivity. Here, we report the synthesis and characterization of two new mixed-valence dilanthanide compounds in this series, (Cp iPr5 ) 2 Ln 2 I 3 (1-Ln; Ln = Ho, Er). Both compounds feature a Ln–Ln bonding interaction, the first such interaction in any molecular compounds of Ho or Er. Like the Tb and Dy congeners, both complexes exhibit high-spin ground states arising from strong spin–spin coupling between the lanthanide 4f electrons and a single σ-type lanthanide–lanthanide bonding electron. Beyond these similarities, however, the magnetic properties of the two compounds diverge. In particular, 1-Er does not exhibit observable magnetic blocking or slow magnetic relaxation, while 1-Ho exhibits magnetic blocking below 28 K, which is the highest temperature among Ho-based single-molecule magnets, and a spin reversal barrier of 556(4) cm –1 . Additionally, variable-field magnetization data collected for 1-Ho reveal a coercive field of greater than 32 T below 8 K, more than 6-fold higher than observed for the bulk magnets SmCo 5 and Nd 2 Fe 14 B, and the highest coercive field reported to date for any single-molecule magnet or molecule-based magnetic material. Multiconfigurational calculations, supported by far-infrared magnetospectroscopy data, reveal that the stark differences in magnetic properties of 1-Ho and 1-Er arise from differences in the local magnetic anisotropy of the lanthanide centers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Discovery and Synthesis of a Family of Boride Altermagnets

Borides are a rich material family. To push the boundaries of borides’ properties and applications into broader fields, we have conducted systematic theoretical and experimental searches for synthesizable phases in ternary borides TM 2 B 2 (T = 3d, M = 4d/5d transition metals). We find that TM 2 B 2 in the FeMo 2 B 2 -type and CoW 2 B 2 -type structures form a large family of stable/metastable materials of 120 members. Among them, we identify 40 materials with stable magnetic solutions. Further, we discover 11 altermagnets in the FeMo 2 B 2 -type structure. So far, boride altermagnets are rare. In these altermagnets, T = Fe or Mn atoms are arranged in parallel T-chains with strong ferromagnetic intrachain couplings and antiferromagnetic interchain couplings. They simultaneously exhibit electronic band spin splitting, typical of ferromagnetism, and zero net magnetization, typical of antiferromagnetism. They also exhibit magnonic band chiral splitting. Both effects originate from the unique altermagnetic symmetries crucially constrained by the nonmagnetic atoms in the structure. Transport properties of relevance to spintronic applications, including the strain-induced spin-splitter effect and anomalous Hall effect, are predicted. An iodine-assisted synthesis method for TM 2 B 2 is developed, using which 7 of the predicted low-energy phases are experimentally synthesized and characterized, including 4 altermagnets. This work expands the realm of borides by offering new opportunities for studying altermagnetism and altermagnons in borides. It also provides valuable insights into the discovery and design of altermagnets. Here, by demonstrating that altermagnets can exist as families sharing a common motif, this work paves a feasible route for discovering altermagnets by elemental substitutions and high-throughput computations.

Chemical structure↗

Predicted Ferromagnetism in Discovered Co–Bi Binary Phases

Binary solid-state materials offer unique insight into how the interplay of factors such as stoichiometry and bonding interactions affects magnetism and electronic properties. In this work, we considered systems where a transition metal provides the spin moment and a heavy main group element bolsters strong spin–orbit coupling. Within this context, cobalt, a known component of permanent magnets, and bismuth, functionally the heaviest element stable to radioactive decay, form a compelling combination. The Co–Bi system has been previously shown to exhibit superconductivity in a phase recovered from high pressure. We expected the Co−Bi system could also be ferromagnetic, resulting in two sets of compounds within one chemical system, one superconducting and one ferromagnetic. Subsequently, we investigated the Co–Bi system through both experimental and theoretical approaches to discover new candidates for permanent magnets. Ab initio random structure searching calculations identified five new compounds with diverse structural motifs that may form at higher pressures than previously reported. Experimental high-pressure synthesis yielded four compounds: α-CoBi, α-CoBi 2 , β-CoBi, and β-CoBi 2 . Three of these phases, α-CoBi 2 , β-CoBi, and β-CoBi 2 , were consistent with the calculated structures, corresponding to a 60% success rate for our structure search and underscoring the strength of combining computation with experiment. Theory predicts β-CoBi and β-CoBi2 are ferromagnetic, with β-CoBi possessing larger magnetocrystalline anisotropy energy than familiar permanent magnets such as CoPt and Nd–Fe–B. These results suggest the Co–Bi system could be a platform for understanding the factors that underpin magnetism and, to an extent, superconductivity in a chemically simple binary system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mechanistic Insight into Tunable Spin Relaxation in Two-Dimensional Type-II Ligand-Perovskite Heterostructures

Two-dimensional (2D) metal-halide perovskites with spin-dependent optical properties hold great promise for spintronic and quantum applications. However, their spin lifetimes, especially for n = 1 2D perovskites, are typically limited to subpicosecond time scales due to rapid spin relaxation driven by strong spin−orbit coupling (SOC), electron−hole exchange interactions, and phonon-mediated scattering. Here, we demonstrate that type-II ligand-perovskite heterostructures overcome these constraints by reducing electron−hole wave function overlap and exciton binding energy. Compared to the type-I 2D perovskite (PEA) 2 PbI 4 with a spin lifetime of 0.29 ps at room temperature, our engineered type-II systems achieve substantially extended spin lifetimes, ∼6.37 ps for (4Tm) 2 PbI 4 and ∼18.47 ps for (4TCNm) 2 PbI 4 . In both materials, spatial charge separation across the perovskite−ligand interface mitigates the Bir−Aronov− Pikus (BAP) mechanism. Temperature- and fluence-dependent measurements reveal Elliott−Yafet (EY)-dominated spin relaxation in (4Tm) 2 PbI 4 , consistent with the observation of coherent phonon oscillation, whereas (4TCNm) 2 PbI 4 exhibits D’yakonov−Perel (DP)-dominated spin relaxation, with weaker phonon coupling further suppressing the EY relaxation, enabling spin lifetimes up to ∼126.81 ps at 5 K. Our findings establish a structural design framework for tailoring spin dynamics in 2D perovskites, offering a promising strategy to engineering spin and optoelectronic properties via rational ligand engineering.

Excitons↗

Modulation of the Electronic and Vibrational Landscape in Lead Organic Chalcogenides

Metal organic chalcogenides (MOCs) are an emerging class of two-dimensional (2D) materials featuring tunable band gaps and strong light-matter interactions with great potential for optical and polaritonic applications. Lead organic chalcogenides (LOCs) stand out among MOCs for sustaining long-lived coherent optical phonons despite their distorted lattices. However, the strong electron–phonon coupling also leads to rapid charge carrier self-trapping, hindering carrier transport. Herein, we demonstrate that charge carrier self-trapping is suppressed in Se- and Te-based LOCs. Specifically, the expansive Se and Te orbitals give rise to more dispersive conduction bands and reduced electron effective masses, thereby mitigating carrier self-trapping. As a result of reduced carrier self-trapping, the Se- and Te-based LOCs exhibit enhanced band-to-band photoluminescence and improved charge transport performance. Furthermore, our results provide a synthetic route to Se- and Te-based LOC single crystals and demonstrate the potential of orbital engineering to tune their electronic and phononic properties.

Chalcogenides↗

Genome-scale metabolic rewiring improves titers rates and yields of the non-native product indigoidine at scale

Abstract High titer, rate, yield (TRY), and scalability are challenging metrics to achieve due to trade-offs between carbon use for growth and production. To achieve these metrics, we take the minimal cut set (MCS) approach that predicts metabolic reactions for elimination to couple metabolite production strongly with growth. We compute MCS solution-sets for a non-native product indigoidine, a sustainable pigment, in Pseudomonas putida KT2440, an emerging industrial microbe. From the 63 solution-sets, our omics guided process identifies one experimentally feasible solution requiring 14 simultaneous reaction interventions. We implement a total of 14 genes knockdowns using multiplex-CRISPRi. MCS-based solution shifts production from stationary to exponential phase. We achieve 25.6 g/L, 0.22 g/l/h, and ~50% maximum theoretical yield (0.33 g indigoidine/g glucose). These phenotypes are maintained from batch to fed-batch mode, and across scales (100-ml shake flasks, 250-ml ambr®, and 2-L bioreactors).

59 BASIC BIOLOGICAL SCIENCES↗

Additive manufacturing of strong silica sand structures enabled by polyethyleneimine binder

Abstract Binder Jet Additive Manufacturing (BJAM) is a versatile AM technique that can form parts from a variety of powdered materials including metals, ceramics, and polymers. BJAM utilizes inkjet printing to selectively bind these powder particles together to form complex geometries. Adoption of BJAM has been limited due to its inability to form strong green parts using conventional binders. We report the discovery of a versatile polyethyleneimine (PEI) binder for silica sand that doubled the flexural strength of parts to 6.28 MPa compared with that of the conventional binder, making it stronger than unreinforced concrete (~4.5 MPa) in flexural loading. Furthermore, we demonstrate that PEI in the printed parts can be reacted with ethyl cyanoacrylate through a secondary infiltration, resulting in an increase in flexural strength to 52.7 MPa. The strong printed parts coupled with the ability for sacrificial washout presents potential to revolutionize AM in various applications including construction and tooling.

36 MATERIALS SCIENCE↗

Trade off-free entanglement stabilization in a superconducting qutrit-qubit system

Abstract Quantum reservoir engineering is a powerful framework for autonomous quantum state preparation and error correction. However, traditional approaches to reservoir engineering are hindered by unavoidable coherent leakage out of the target state, which imposes an inherent trade off between achievable steady-state state fidelity and stabilization rate. In this work we demonstrate a protocol that achieves trade off-free Bell state stabilization in a qutrit-qubit system realized on a circuit-QED platform. We accomplish this by creating a purely dissipative channel for population transfer into the target state, mediated by strong parametric interactions coupling the second-excited state of a superconducting transmon and the engineered bath resonator. Our scheme achieves a state preparation fidelity of 84% with a stabilization time constant of 339 ns, leading to a 54 ns error-time product in a solid-state quantum information platform.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Nonreciprocal directional dichroism of a chiral magnet in the visible range

Nonreciprocal directional dichroism is an unusual light–matter interaction that gives rise to diode-like behavior in low-symmetry materials. The chiral varieties are particularly scarce due to the requirements for strong spin–orbit coupling, broken time-reversal symmetry, and a chiral axis. Here we bring together magneto-optical spectroscopy and first-principles calculations to reveal high-energy, broadband nonreciprocal directional dichroism in Ni 3 TeO 6 with special focus on behavior in the metamagnetic phase above 52 T. In addition to demonstrating this effect in the magnetochiral configuration, we explore the transverse magnetochiral orientation in which applied field and light propagation are orthogonal to the chiral axis and, by so doing, uncover an additional configuration with a unique nonreciprocal response in the visible part of the spectrum. In a significant conceptual advance, we use first-principles methods to analyze how the Ni 2+ d-to-d on-site excitations develop magneto-electric character and present a microscopic model that unlocks the door to theory-driven discovery of chiral magnets with nonreciprocal properties.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Odd- and even-denominator fractional quantum Hall states in monolayer WSe 2

Monolayer semiconducting transition-metal dichalcogenides (TMDs) represent a unique class of two-dimensional (2D) electron systems. Their atomically thin structure facilitates gate tunability just like graphene does, but unlike graphene, TMDs have the advantage of a sizable band gap and strong spin–orbit coupling. Measurements under large magnetic fields have revealed an unusual Landau level (LL) structure, distinct from other 2D electron systems. However, owing to the limited sample quality and poor electrical contact, probing the lowest LLs has been challenging, and observation of electron correlations within the fractionally filled LL regime has not been possible. Here, through bulk electronic compressibility measurements, we investigate the LL structure of monolayer WSe 2 in the extreme quantum limit, and observe fractional quantum Hall states in the lowest three LLs. The odd-denominator fractional quantum Hall sequences demonstrate a systematic evolution with the LL orbital index, consistent with generic theoretical expectations. In addition, we observe an even-denominator state in the second LL that is expected to host non-Abelian statistics. Finally, our results suggest that the 2D semiconductors can provide an experimental platform that closely resembles idealized theoretical models in the quantum Hall regime.

36 MATERIALS SCIENCE↗

Weyl, Dirac and high-fold chiral fermions in topological quantum matter

Quantum materials hosting Weyl fermions have opened a new era of research in condensed matter physics. First proposed in 1929 in the context of particle physics, Weyl fermions have yet to be observed as elementary particles. In 2015, Weyl fermions were detected as collective electronic excitations in the strong spin–orbit coupled material tantalum arsenide, TaAs. This discovery was followed by a flurry of experimental and theoretical explorations of Weyl phenomena in materials. Weyl materials naturally lend themselves to the exploration of the topological index associated with Weyl fermions and their divergent Berry curvature field, as well as the topological bulk–boundary correspondence, giving rise to protected conducting surface states. Here, we review the broader class of Weyl topological phenomena in materials, starting with the observation of emergent Weyl fermions in the bulk and Fermi arc states on the surface of the TaAs family of crystals by photoemission spectroscopy. We then discuss several exotic optical and magnetic responses observed in these materials, as well as progress in developing related chiral materials. We discuss the conceptual development of high-fold chiral fermions, which generalize Weyl fermions, and we review the observation of high-fold chiral fermion phases by taking the rhodium silicide, RhSi, family of crystals as a prime example. Lastly, we discuss recent advances in Weyl line phases in magnetic topological materials. With this Review, we aim to provide an introduction to the basic concepts underlying Weyl physics in condensed matter, and to representative materials and their electronic structures and topology as revealed by spectroscopic studies. Finally, we hope this work serves as a guide for future theoretical and experimental explorations of chiral fermions and related topological quantum systems with potentially enhanced functionalities.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Study of the magnetic interface and its effect in Fe/NiFe bilayers of alternating order

We present a comprehensive study on the magnetization reversal in the Fe/NiFe bilayer system by alternating the order of the magnetic layers. All the samples show growth-induced uniaxial magnetic anisotropy due to the oblique angle deposition technique. Strong interfacial exchange coupling between the Fe and NiFe layers leads to single-phase hysteresis loops in the bilayer system. The strength of coupling being dependent on the interface changes upon alternating the order of magnetic layers. The magnetic parameters such as coercivity H C , and anisotropy field H K become almost doubled when a NiFe layer is grown over the Fe layers. This enhancement in the magnetic parameters is primarily dependent on the increase of the thickness and magnetic moment of the Fe–NiFe interfacial layer as revealed from the polarized neutron reflectivity (PNR) data of the bilayer samples. The difference in the thickness and magnetization of the Fe–NiFe interfacial layer indicates the modification of the microstructure by alternating the order of the magnetic layers of the bilayers. The interfacial magnetic moment increased by almost 18% when the NiFe layer was grown over the Fe layer. In spite of the different values of anisotropy fields and modified interfacial exchange coupling, the Gilbert damping constant values of the ferromagnetic bilayers remain similar to the single NiFe layer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗