Highly Efficient Spin Injection and Readout Across Van Der Waals Interface.

Spin injection, transport, and detection across the interface between a ferromagnet and a spin-carrying channel are crucial for energy-efficient spin logic devices. However, interfacial conductance mismatch, spin dephasing, and inefficient spin-to-charge conversion significantly reduce the efficiency of these processes. In this study, it is demonstrated that an all van der Waals heterostructure consisting of a ferromagnet (Fe3GeTe2) and Weyl semimetal enables a large spin readout efficiency. Specifically, a nonlocal spin readout signal of 150 mΩ and a local spin readout signal of 7.8 Ω is achieved, which reach the signal level useful for practical spintronic devices. The remarkable spin readout signal is attributed to suppressed spin dephasing channels at the vdW interfaces, long spin diffusion, and efficient charge-spin interconversion in Td-MoTe2. These findings highlight the potential of vdW heterostructures for spin Hall effect-enabled spin detection with high efficiency, opening up new possibilities for spin-orbit logic devices using vdW interfaces.

Air-Stable Wafer-Scale Ferromagnetic Metallo-Carbon Nitride Monolayer.

The pursuit of robust, long-range magnetic ordering in two-dimensional (2D) materials holds immense promise for driving technological advances. However, achieving this goal remains a grand challenge due to enhanced quantum and thermal fluctuations as well as chemical instability in the 2D limit. While magnetic ordering has been realized in atomically thin flakes of transition metal chalcogenides and metal halides, these materials often suffer from air instability. In contrast, 2D carbon-based materials are stable enough, yet the challenge lies in creating a high density of local magnetic moments and controlling their long-range magnetic ordering. Here, we report a novel wafer-scale synthesis of an air-stable metallo-carbon nitride monolayer (MCN, denoted as MN4/CNx), featuring ultradense single magnetic atoms and exhibiting robust room-temperature ferromagnetism. Under low-pressure chemical vapor deposition conditions, thermal dehydrogenation and polymerization of metal phthalocyanine (MPc) on copper foil at elevated temperature generate a substantial number of nitrogen coordination sites for anchoring magnetic single atoms in monolayer MN4/CNx (where M = Fe, Co, and Ni). The incorporation of densely populating MN4 sites into monolayer MCN networks leads to robust ferromagnetism up to room temperature, enabling the observation of anomalous Hall effects with excellent chemical stability. Detailed electronic structure calculations indicate that the presence of high-density metal sites results in the emergence of spin-split d-bands near the Fermi level, causing a favorable long-range ferromagnetic exchange coupling through direct exchange interactions. Our work demonstrates a novel synthesis approach for wafer-scale MCN monolayers with robust room-temperature ferromagnetism and may shed light on practical electronic and spintronic applications.

Expedient alkyne semi-hydrogenation by using a bimetallic AgCu-C3N4 single atom catalyst.

Metal-catalyzed semi-hydrogenation of alkynes is an important step in organic synthesis to produce diverse chemical compounds. However, conventional noble metal catalysts often suffer from poor selectivity owing to over-hydrogenation. Here, we demonstrate a high-loading bimetallic AgCu-C3N4 single-atom catalyst (SAC) for alkyne semi-hydrogenation. The AgCu-C3N4 SACs exhibit higher activity and selectivity (99%) than their low-loading variants due to the synergistic interaction of heteronuclear Ag-Cu sites at small inter-site distances. Using a combination of techniques such as phenylacetylene-DRIFTS, H2-temperature programmed desorption and DFT calculations, we showed that the cooperative bimetallic interaction during alkyne semi-hydrogenation was achieved by isolated Ag centers as hydrogen activation sites and isolated Cu centers as alkyne activation sites. Our work highlights the importance of achieving high catalyst loading to reduce the inter-site distance in bimetallic SACs for cooperative interactions, which can potentially open new catalytic pathways for synthesizing fine chemicals and pharmaceuticals.

Chiral multiferroicity in two-dimensional hybrid organic-inorganic perovskites.

Chiral multiferroics offer remarkable capabilities for controlling quantum devices at multiple levels. However, these materials are rare due to the competing requirements of long-range orders and strict symmetry constraints. In this study, we present experimental evidence that the coexistence of ferroelectric, magnetic orders, and crystallographic chirality is achievable in hybrid organic-inorganic perovskites [(R/S)-ß-methylphenethylamine]2CuCl4. By employing Landau symmetry mode analysis, we investigate the interplay between chirality and ferroic orders and propose a novel mechanism for chirality transfer in hybrid systems. This mechanism involves the coupling of non-chiral distortions, characterized by defining a pseudo-scalar quantity, ξ = p ⋅ r ( p represents the ferroelectric displacement vector and r denotes the ferro-rotational vector), which distinguishes between (R)- and (S)-chirality based on its sign. Moreover, the reversal of this descriptor's sign can be associated with coordinated transitions in ferroelectric distortions, Jahn-Teller antiferro-distortions, and Dzyaloshinskii-Moriya vectors, indicating the mediating role of crystallographic chirality in magnetoelectric correlations.

Two-dimensional chiral perovskites with large spin Hall angle and collinear spin Hall conductivity.

Two-dimensional hybrid organic-inorganic perovskites with chiral spin texture are emergent spin-optoelectronic materials. Despite the wealth of chiro-optical studies on these materials, their charge-to-spin conversion efficiency is unknown. We demonstrate highly efficient electrically driven charge-to-spin conversion in enantiopure chiral perovskites (R/S-MB)2(MA)3Pb4I13 (〈n〉 = 4), where MB is 2-methylbutylamine, MA is methylamine, Pb is lead, and I is iodine. Using scanning photovoltage microscopy, we measured a spin Hall angle θsh of 5% and a spin lifetime of ~75 picoseconds at room temperature in 〈n〉 = 4 chiral perovskites, which is much larger than its racemic counterpart as well as the lower 〈n〉 homologs. In addition to current-induced transverse spin current, the presence of a coexisting out-of-plane spin current confirms that both conventional and collinear spin Hall conductivities exist in these low-dimensional crystals.

High yield electrosynthesis of oxygenates from CO using a relay Cu-Ag co-catalyst system.

As a sustainable alternative to fossil fuel-based manufacture of bulk oxygenates, electrochemical synthesis using CO and H2O as raw materials at ambient conditions offers immense appeal. However, the upscaling of the electrosynthesis of oxygenates encounters kinetic bottlenecks arising from the competing hydrogen evolution reaction with the selective production of ethylene. Herein, a catalytic relay system that can perform in tandem CO capture, activation, intermediate transfer and enrichment on a Cu-Ag composite catalyst is used for attaining high yield CO-to-oxygenates electrosynthesis at high current densities. The composite catalyst Cu/30Ag (molar ratio of Cu to Ag is 7:3) enables high efficiency CO-to-oxygenates conversion, attaining a maximum partial current density for oxygenates of 800 mA cm-2 at an applied current density of 1200 mA cm-2, and with 67 % selectivity. The ability to finely control the production of ethylene and oxygenates highlights the principle of efficient catalyst design based on the relay mechanism.

Beyond Conventional Charge Density Wave for Strongly Enhanced 2D Superconductivity in 1H-TaS2 Superlattices.

Noncentrosymmetric transition metal dichalcogenide (TMD) monolayers offer a fertile platform for exploring unconventional Ising superconductivity (SC) and charge density waves (CDWs). However, the vulnerability of isolated monolayers to structural disorder and environmental oxidation often degrade their electronic coherence. Herein, an alternative approach is reported for fabricating stable and intrinsic monolayers of 1H-TaS2 sandwiched between SnS blocks in a (SnS)1.15TaS2 van der Waals (vdW) superlattice. The SnS block layers not only decouple individual 1H-TaS2 sublayers to endow them with monolayer-like electronic characteristics, but also protect the 1H-TaS2 layers from electronic degradation. The results reveal the characteristic 3 × 3 CDW order in 1H-TaS2 sublayers associated with electronic rearrangement in the low-lying sulfur p band, which uncovers a previously undiscovered CDW mechanism rather than the conventional Fermi surface-related framework. Additionally, the (SnS)1.15TaS2 superlattice exhibits a strongly enhanced Ising-like SC with a layer-independent Tc of ≈3.0 K, comparable to that of the isolated monolayer 1H-TaS2 sample, presumably attributed to their monolayer-like characteristics and retained Fermi states. These results provide new insights into the long-debated CDW order and enhanced SC of monolayer 1H-TaS2, establishing bulk vdW superlattices as promising platforms for investigating exotic collective quantum phases in the 2D limit.

Molecularly thin, two-dimensional all-organic perovskites.

Recently, the emergence of all-organic perovskites with three-dimensional (3D) structures has expanded the potential applications of perovskite materials. However, the synthesis and utilization of all-organic perovskites in 2D form remain largely unexplored because the design principle has not been developed. We present the successful synthesis of a metal-free 2D layered perovskite, denoted as the Choi-Loh van der Waals phase (CL-v phase), with the chemical formula A2B2X4, where A represents a larger-sized cation compared to B and X denotes an anion. The CL-v phase exhibits a van der Waals gap enabled by interlayer hydrogen bonding and can be exfoliated or grown as molecularly thin 2D organic crystals. The dielectric constants of the CL-v phase range from 4.8 to 5.5 and we demonstrate their potential as gate dielectrics for thin-film transistors.

Nonlinear transport and radio frequency rectification in BiTeBr at room temperature.

Materials showing second-order nonlinear transport under time reversal symmetry can be used for Radio Frequency (RF) rectification, but practical application demands room temperature operation and sensitivity to microwatts level RF signals in the ambient. In this study, we demonstrate that BiTeBr exhibits a giant nonlinear response which persists up to 350 K. Through scaling and symmetry analysis, we show that skew scattering is the dominant mechanism. Additionally, the sign of the nonlinear response can be electrically switched by tuning the Fermi energy. Theoretical analysis suggests that the large Rashba spin-orbit interactions (SOI), which gives rise to the chirality of the Bloch electrons, provide the microscopic origin of the observed nonlinear response. Our BiTeBr rectifier is capable of rectifying radiation within the frequency range of 0.2 to 6 gigahertz at room temperature, even at extremely low power levels of -15 dBm, and without the need for external biasing. Our work highlights that materials exhibiting large Rashba SOI have the potential to exhibit nonlinear responses at room temperature, making them promising candidates for harvesting high-frequency and low-power ambient electromagnetic energy.

Promoted Growth and Multiband Emission in Heterostructured Perovskites Through Cs+ -Sublattice Interaction.

Precise control of exciton confinement in metal halide perovskites is critical to the development of high-performance, stable optoelectronic devices. A significant hurdle is the swift completion of ionic metathesis reactions, often within seconds, making consistent control challenging. Herein, the introduction of different steric hindrances in a Cs+ sublattice within CsYb2 F7 is reported, which effectively modulates the reaction rate of Cs+ with lead (Pb2+ ) and halide ions in solution, extending the synthesis time for perovskite nanostructures to tens of minutes. Importantly, the Cs+ sublattice provides a crystal facet-dependent preference for perovskite growth and thus exciton confinement, allowing the simultaneous occurrence of up to six emission bands of CsPbBr3 . Moreover, the rigid CsYb2 F7 nano template offers high activation energy and enhances the stability of the resulting perovskite nanostructures. This methodology provides a versatile approach to synthesizing functional heterostructures. Its robustness is demonstrated by in-situ growth of perovskite nanostructures on Cs+ -mediated metal-organic frameworks.

Ferroics in Hybrid Organic-Inorganic Perovskites: Fundamentals, Design Strategies, and Implementation.

Hybrid organic-inorganic perovskites (HOIPs) afford highly versatile structure design and lattice dimensionalities; thus, they are actively researched as material platforms for the tailoring of ferroic behaviors. Unlike single-phase organic or inorganic materials, the interlayer coupling between organic and inorganic components in HOIPs allows the modification of strain and symmetry by chirality transfer or lattice distortion, thereby enabling the coexistence of ferroic orders. This review focuses on the principles for engineering one or multiple ferroic orders in HOIPs, and the conditions for achieving multiferroicity and magnetoelectric properties. The prospects of multilevel ferroic modulation, chiral spin textures, and spin orbitronics in HOIPs are also presented.

In-Plane Ferrielectric Order in van der Waals ß'-In2Se3.

van der Waals ferroic materials exhibit rich potential for implementing future generation functional devices. Among these, layered ß'-In2Se3 has fascinated researchers with its complex superlattice and domain structures. As opposed to ferroelectric α-In2Se3, the understanding of ß'-In2Se3 ferroic properties remains unclear because ferroelectric, antiferroelectric, and ferroelastic characteristics have been separately reported in this material. To develop useful applications, it is necessary to understand the microscopic structural properties and their correlation with macroscopic device characteristics. Herein, using scanning transmission electron microscopy (STEM), we observed that the arrangement of dipoles deviates from the ideal double antiparallel antiferroelectric character due to competition between antiferroelectric and ferroelectric structural ordering. By virtue of second-harmonic generation, four-dimensional STEM, and in-plane piezoresponse force microscopy, the long-range inversion-breaking symmetry, uncompensated local polarization, and net polarization domains are unambiguously verified, revealing ß'-In2Se3 as an in-plane ferrielectric layered material. Additionally, our device study reveals analogous resistive switching behaviors of different types owing to polarization switching, defect migration, and defect-induced charge trapping/detrapping processes.

Heteroepitaxial Growth of Black Phosphorus on Tin Monosulfide.

Black phosphorus (Black P), a layered semiconductor with a layer-dependent bandgap and high carrier mobility, is a promising candidate for next-generation electronics and optoelectronics. However, the synthesis of large-area, layer-precise, single crystalline Black P films remains a challenge due to their high nucleation energy. Here, we report the molecular beam heteroepitaxy of single crystalline Black P films on a tin monosulfide (SnS) buffer layer grown on Au(100). The layer-by-layer growth mode enables the preparation of monolayer to trilayer films, with band gaps that reflect layer-dependent quantum confinement.

Ammonia Electrosynthesis from Nitrate Using a Ruthenium-Copper Cocatalyst System: A Full Concentration Range Study.

Electrochemical synthesis of ammonia via the nitrate reduction reaction (NO3RR) has been intensively researched as an alternative to the traditional Haber-Bosch process. Most research focuses on the low concentration range representative of the nitrate level in wastewater, leaving the high concentration range, which exists in nuclear and fertilizer wastes, unexplored. The use of a concentrated electrolyte (≥1 M) for higher rate production is hampered by poor hydrogen transfer kinetics. Herein, we demonstrate that a cocatalytic system of Ru/Cu2O catalyst enables NO3RR at 10.0 A in 1 M nitrate electrolyte in a 16 cm2 flow electrolyzer, with 100% faradaic efficiency toward ammonia. Detailed mechanistic studies by deuterium labeling and operando Fourier transform infrared (FTIR) spectroscopy allow us to probe the hydrogen transfer rate and intermediate species on Ru/Cu2O. Ab initio molecular dynamics (AIMD) simulations reveal that adsorbed hydroxide on Ru nanoparticles increases the density of the hydrogen-bonded water network near the Cu2O surface, which promotes the hydrogen transfer rate. Our work highlights the importance of engineering synergistic interactions in cocatalysts for addressing the kinetic bottleneck in electrosynthesis.

Gate-tunable anomalous Hall effect in Bernal tetralayer graphene.

Large spin-orbit coupling is often thought to be critical in realizing magnetic order-locked charge transport such as the anomalous Hall effect (AHE). Recently, artificial stacks of two-dimensional materials, e.g., magic-angle twisted bilayer graphene on hexagonal boron-nitride heterostructures and dual-gated rhombohedral trilayer graphene, have become platforms for realizing AHE without spin-orbit coupling. However, these stacking arrangements are not energetically favorable, impeding experiments and further device engineering. Here we report an anomalous Hall effect in Bernal-stacked tetralayer graphene devices (BTG), the most stable configuration of four-layer graphene. BTG AHE is switched on by a displacement field and is most pronounced at low carrier densities. The onset of AHE occurs in tandem with a full metal to a broken isospin transition indicating an orbital origin of the itinerant ferromagnetism. At lowest densities, BTG exhibits an unconventional hysteresis with step-like anomalous Hall plateaus. Persisting to several tens of kelvin, AHE in BTG demonstrates the ubiquity and robustness of magnetic order in readily available and stable multilayer Bernal graphene stacks-a new venue for intrinsic non-reciprocal responses.

Ion-Conductive Metallo-Covalent Organic Frameworks Constructed with Tridentate Ligand and Zn Nodes.

Metallo-covalent organic frameworks (metallo-COFs) are organometallic scaffolds in which covalently bonded organic frameworks are interwoven with metal-coordinated pendant groups. Unlike the rigid ligands traditionally used for metal coordination, the utilization of "soft" ligands allows for configurable topology and pore structure in metallo-COFs, particularly when the ligands are generated in situ during dynamic synthesis. In this study, we present the rational synthesis of metallo-COFs based on pyridine-2,6-diimine (pdi), wherein the incorporation of Zn2+ ions and in situ-generated tridentate ligands (pdi) yields metallo-COFs with a square-like lattice. In the absence of Zn2+ ions, a topological isomer COF with a Kagome lattice is instead produced. Thus, the presence or absence of Zn2+ ions allows us to switch between two distinct morphologies corresponding to metallo-COF or COF. In comparison to Brønsted acid-catalyzed COF, which necessitates postmetallization for loading metal ions, the metal-templated COF synthesis method yields COFs with improved crystallinity and approximately 1:1 [Zn2+]/ligand composition. Building upon the metal-templated COF synthesis approach, we successfully synthesized pdiCOF-Zn-2 and pdiCOF-Zn-3, which possess square-like and honeycomb lattices, respectively. The enhanced crystallinity and near 1:1 [Zn2+]/ligand composition of pdiCOF-Zn-3 (honeycomb) facilitate its application as ion transport channels.

Electron Spin Decoherence Dynamics in Magnetic Manganese Hybrid Organic-Inorganic Crystals: The Effect of Lattice Dimensionality.

Organic-inorganic metal hybrids with their tailorable lattice dimensionality and intrinsic spin-splitting properties are interesting material platforms for spintronic applications. While the spin decoherence process is extensively studied in lead- and tin-based hybrids, these systems generally show short spin decoherence lifetimes, and their correlation with the lattice framework is still not well-understood. Herein, we synthesized magnetic manganese hybrid single crystals of (4-fluorobenzylamine)2MnCl4, ((R)-3-fluoropyrrolidinium)MnCl3, and (pyrrolidinium)2MnCl4, which represent a change in lattice dimensionality from 2D and 1D to 0D, and studied their spin decoherence processes using continuous-wave electron spin resonance spectroscopy. All manganese hybrids exhibit nanosecond-scale spin decoherence time τ2 dominated by the symmetry-directed spin exchange interaction strengths of Mn2+-Mn2+ pairs, which is much longer than lead- and tin-based metal hybrids. In contrast to the similar temperature variation laws of τ2 in 2D and 0D structures, which first increase and gradually drop afterward, the 1D structure presents a monotonous rise of τ2 with the temperatures, indicating the strong correlation of spin decoherence with the lattice rigidity of the inorganic framework. This is also rationalized on the basis that the spin decoherence is governed by the competitive contributions from motional narrowing (prolonging the τ2) and electron-phonon coupling interaction (shortening the τ2), both of which are thermally activated, with the difference that the former is more pronounced in rigid crystalline lattices.

Interplay of the charge density wave transition with topological and superconducting properties.

Exotic phenomena due to the interplay of different quantum orders have been observed and the study of these phenomena has emerged as a new frontier in condensed matter research, especially in the two-dimensional limit. Here, we report the coexistence of charge density waves (CDWs), superconductivity, and nontrivial topology in monolayer 1H-MSe2 (M = Nb, Ta) triggered by momentum-dependent electron-phonon coupling through electron doping. At a critical electron doping concentration, new 2 × 2 CDW phases emerge with nontrivial topology, Dirac cones, and van Hove singularities. Interestingly, these 2 × 2 CDW phases are also superconducting. Our findings not only reveal a route towards realizing nontrivial electronic characters by CDW engineering, but also provide an exciting platform to modulate different quantum states at the confluence of CDWs, superconductivity, nontrivial topology, and electron-phonon coupling.

Near-90° Switch in the Polar Axis of Dion-Jacobson Perovskites by Halide Substitution.

Ferroelectricity in two-dimensional hybrid (2D) organic-inorganic perovskites (HOIPs) can be engineered by tuning the chemical composition of the organic or inorganic components to lower the structural symmetry and order-disorder phase change. Less efforts are made toward understanding how the direction of the polar axis is affected by the chemical structure, which directly impacts the anisotropic charge order and nonlinear optical response. To date, the reported ferroelectric 2D Dion-Jacobson (DJ) [PbI4]2- perovskites exhibit exclusively out-of-plane polarization. Here, we discover that the polar axis in ferroelectric 2D Dion-Jacobson (DJ) perovskites can be tuned from the out-of-plane (OOP) to the in-plane (IP) direction by substituting the iodide with bromide in the lead halide layer. The spatial symmetry of the nonlinear optical response in bromide and iodide DJ perovskites was probed by polarized second harmonic generation (SHG). Density functional theory calculations revealed that the switching of the polar axis, synonymous with the change in the orientation of the sum of the dipole moments (DMs) of organic cations, is caused by the conformation change of organic cations induced by halide substitution.

Polymorphism and Ferroelectricity in Indium(III) Selenide.

Two-dimensional indium(III) selenide (In2Se3) is characterized by rich polymorphism and offers the prospect of overcoming thickness-related depolarization effects in conventional ferroelectrics. α-In2Se3 has attracted attention as a ferroelectric semiconductor that can retain ferroelectricity at the monolayer level; thus, it can be potentially deployed in high density memory switching modes that bypasses the traditional von Neumann architecture in device design. However, studies involving α-In2Se3 are often hindered by difficulties in phase identification owing to mixing with ß-In2Se3. ß-In2Se3 has several polymorphs, among which include the antiferroelectric and ferroelastic ß'-In2Se3. It is important to understand polymorph transitions and crystal-amorphous phase transitions in ß-In2Se3 to tap into the potential of this material for resistive memory storage. In this review, we discuss how the various polymorphs and polytypes of In2Se3 can be rigorously differentiated and further highlight recent applications of these phases in ferroelectrics and memory devices.