Suppression of antiferromagnetic order by strain-enhanced frustration in honeycomb cobaltate.

Layered honeycomb cobaltates are predicted as promising for realizing the Kitaev quantum spin liquid, a many-body quantum entangled ground state characterized by fractional excitations. However, they exhibit antiferromagnetic ordering at low temperatures, hindering the expected quantum state. We demonstrate that controlling the trigonal distortion of CoO6 octahedra is crucial to suppress antiferromagnetic order through enhancing frustration in layered honeycomb cobaltates. Using heterostructure engineering on Cu3Co2SbO6 thin films, we adjust the trigonal distortion of CoO6 octahedra and the resulting trigonal crystal field. The original Néel temperature of 16 kelvin in bulk Cu3Co2SbO6 decreases (increases) to 7.8 kelvin (22.7 kelvin) in strained Cu3Co2SbO6 films by decreasing (increasing) the magnitude of the trigonal crystal fields. The first-principles calculation suggests the enhancement of geometrical frustration as the origin of the suppression of antiferromagnetism. This finding supports the potential of layered honeycomb cobaltate heterostructures and strain engineering in realizing extremely elusive quantum phases of matter.

Assessing the role of cold front passage and synoptic patterns on air pollution in the Korean Peninsula.

Various numerical experiments using WRF (Weather Research & Forecasting Model) and CMAQ (Community Multiscale Air Quality Modeling System) were performed to analyze the phenomenon of rapidly high concentration PM2.5 after the passage of a cold front in an area with limited local emissions. The episode period was from January 14 to 23, 2018, and analysis was conducted by dividing it into two stages according to the characteristics of changes in PM2.5 concentrations during the period. Through the analysis of observational data during the episode period, we confirmed meteorological impacts (decrease in temperature, increase in wind speed and relative humidity) and an increase in air pollution (PM10 and PM2.5) attributed to the passage of a cold front. Using CMAQ's IPR (Integrated Process Rate) analysis, the contribution of the horizontal advection process was observed in transporting PM2.5 to Gangneung at higher altitudes, and the PM2.5 concentrations at the surface increased because the vertical advection process was influenced by the terrain. Notably, in Stage 2 (64 µg·m-3), a higher contribution of the vertical advection process compared to Stage 1 (35 µg·m-3) was observed, which is attributed to the differences in synoptic patterns following the passage of the cold front. During Stage 2, following the cold front, atmospheric stability (dominance of high-pressure system) led to air subsidence and the presence of a temperature inversion layer, creating favorable meteorological conditions for the accumulation of air pollutants. This study offers the mechanisms of air pollution over the Korean Peninsula under non-stationary meteorological conditions, particularly in relation to the passage of the cold front (low-pressure system). Notably, the influence of a cold front can vary according to the synoptic patterns that develop following its passage.

3D microprinting of inorganic porous materials by chemical linking-induced solidification of nanocrystals.

Three-dimensional (3D) microprinting is considered a next-generation manufacturing process for the production of microscale components; however, the narrow range of suitable materials, which include mainly polymers, is a critical issue that limits the application of this process to functional inorganic materials. Herein, we develop a generalised microscale 3D printing method for the production of purely inorganic nanocrystal-based porous materials. Our process is designed to solidify all-inorganic nanocrystals via immediate dispersibility control and surface linking-induced interconnection in the nonsolvent linker bath and thereby creates multibranched gel networks. The process works with various inorganic materials, including metals, semiconductors, magnets, oxides, and multi-materials, not requiring organic binders or stereolithographic equipment. Filaments with a diameter of sub-10 µm are printed into designed complex 3D microarchitectures, which exhibit full nanocrystal functionality and high specific surface areas as well as hierarchical porous structures. This approach provides the platform technology for designing functional inorganics-based porous materials.

Hexaazatriphenylene-Based Two-Dimensional Conductive Covalent Organic Framework with Anisotropic Charge Transfer.

The development of covalent organic frameworks (COFs) with efficient charge transport is of immense interest for applications in optoelectronic devices. To enhance COF charge transport properties, electroactive building blocks and dopants can be used to induce extended conduction channels. However, understanding their intricate interplay remains challenging. We designed and synthesized a tailor-made COF structure with electroactive hexaazatriphenylene (HAT) core units and planar dioxin (D) linkages, denoted as HD-COF. With the support of theoretical calculations, we found that the HAT units in the HD-COF induce strong, eclipsed π-π stacking. The unique stacking of HAT units and the weak in-plane conjugation of dioxin linkages leads to efficient anisotropic charge transport. We fabricated HD-COF films to minimize the grain boundary effect of bulk COFs, which resulted in enhanced conductivity. As a result, the HD-COF films showed an electrical conductivity as high as 1.25 S cm-1 after doping with tris(4-bromophenyl)ammoniumyl hexachloroantimonate.

Dual Catalytic and Self-Assembled Growth of Two-Dimensional Transition Metal Dichalcogenides Through Simultaneous Predeposition Process.

The recent introduction of alkali metal halide catalysts for chemical vapor deposition (CVD) of transition metal dichalcogenides (TMDs) has enabled remarkable two-dimensional (2D) growth. However, the process development and growth mechanism require further exploration to enhance the effects of salts and understand the principles. Herein, simultaneous predeposition of a metal source (MoO3 ) and salt (NaCl) by thermal evaporation is adopted. As a result, remarkable growth behaviors such as promoted 2D growth, easy patterning, and potential diversity of target materials can be achieved. Step-by-step spectroscopy combined with morphological analyses reveals a reaction path for MoS2 growth in which NaCl reacts separately with S and MoO3 to form Na2 SO4 and Na2 Mo2 O7 intermediates, respectively. These intermediates provide a favorable environment for 2D growth, including an enhanced source supply and liquid medium. Consequently, large grains of monolayer MoS2 are formed by self-assembly, indicating the merging of small equilateral triangular grains on the liquid intermediates. This study is expected to serve as an ideal reference for understanding the principles of salt catalysis and evolution of CVD in the preparation of 2D TMDs.

Air-stable van der Waals PtTe2 conductors with high current-carrying capacity and strong spin-orbit interaction.

High-performance van der Waals (vdW) integrated electronics and spintronics require reliable current-carrying capacity. However, it is challenging to achieve high current density and air-stable performance using vdW metals owing to the fast electrical breakdown triggered by defects or oxidation. Here, we report that spin-orbit interacted synthetic PtTe2 layers exhibit significant electrical reliability and robustness in ambient air. The 4-nm-thick PtTe2 synthesized at a low temperature (∼400°C) shows intrinsic metallic transport behavior and a weak antilocalization effect attributed to the strong spin-orbit scattering. Remarkably, PtTe2 sustains a high current density approaching ≈31.5 MA cm-2, which is the highest value among electrical interconnect candidates under oxygen exposure. Electrical failure is caused by the Joule heating of PtTe2 rather than defect-induced electromigration, which was achievable by the native TeOx passivation. The high-quality growth of PtTe2 and the investigation of its transport behaviors lay out essential foundations for the development of emerging vdW spin-orbitronics.

Enhancement of the Rashba Effect in a Conducting SrTiO3 Surface by MoO3 Capping.

Systems having inherent structural asymmetry retain the Rashba-type spin-orbit interaction, which ties the spin and momentum of electrons in the band structure, leading to coupled spin and charge transport. One of the electrical manifestations of the Rashba spin-orbit interaction is nonreciprocal charge transport, which could be utilized for rectifying devices. Further tuning of the Rashba spin-orbit interaction allows additional functionalities in spin-orbitronic applications. In this work, we present our study of nonreciprocal charge transport in a conducting SrTiO3 (001) surface and its significant enhancement by a capping layer. The conductive strontium titanate SrTiO3 (STO) (001) surface was created through oxygen vacancies by Ar+ irradiation, and the nonreciprocal signal was probed by angle- and magnetic field-dependent second harmonic voltage measurement with an AC current. We observed robust directional transport in the Ar+-irradiated sample at low temperatures. The magnitude of the nonreciprocal signal is highly dependent on the irradiation time as it affects the depth of the conducting layer and the impact of the topmost conducting layer. Moreover, the nonreciprocal resistance was significantly enhanced by simply adding a MoO3 capping layer on the conductive STO surface. These results show a simple methodology for tuning and investigating the Rashba effect in a conductive STO surface, which could be adopted for various two-dimensional (2D) conducting layers for spin-orbitronic applications.

Numerical study on advective fog formation and its characteristic associated with cold water upwelling.

Recent rapid industrial development in the Korean Peninsula has increased the impacts of meteorological disasters on marine and coastal environments. In particular, marine fog driven by summer cold water masses can inhibit transport and aviation; yet a lack of observational data hinders our understanding of this phenomena. The present study aimed to analyze the differences in cold water mass formation according to sea surface temperature (SST) resolution and its effects on the occurrence and distribution of sea fog over the Korean Peninsula from June 23-July 1, 2016, according to the Weather Research and Forecasting model. Data from the Final Operational Model Global Tropospheric Analyses were provided at 1° and 0.25° resolutions and NOAA real-time global SST (RTG-SST) data were provided at 0.083°. While conventional analyses have used initial SST distributions throughout the entire simulation period, small-scale, rapidly developing oceanic phenomena (e.g., cold water masses) lasting for several days act as an important mediating factor between the lower atmosphere and sea. RTG-SST was successful at identifying fog presence and maintained the most extensive horizontal distribution of cold water masses. In addition, it was confirmed that the difference in SST resolution led to varying sizes and strengths of the warm pools that provided water vapor from the open sea area to the atmosphere. On examining the horizontal water vapor transport and the vertical structure of the generated sea fog using the RTG-SST, water vapors were found to be continuously introduced by the southwesterly winds from June 29 to 30, creating a fog event throughout June 30. Accordingly, high-resolution SST data must be input into numerical models whenever possible. It is expected that the findings of this study can contribute to the reduction of ship accidents via the accurate simulation of sea fog.

Defect-gradient-induced Rashba effect in van der Waals PtSe2 layers.

Defect engineering is one of the key technologies in materials science, enriching the modern semiconductor industry and providing good test-beds for solid-state physics. While homogenous doping prevails in conventional defect engineering, various artificial defect distributions have been predicted to induce desired physical properties in host materials, especially associated with symmetry breakings. Here, we show layer-by-layer defect-gradients in two-dimensional PtSe2 films developed by selective plasma treatments, which break spatial inversion symmetry and give rise to the Rashba effect. Scanning transmission electron microscopy analyses reveal that Se vacancies extend down to 7 nm from the surface and Se/Pt ratio exhibits linear variation along the layers. The Rashba effect induced by broken inversion symmetry is demonstrated through the observations of nonreciprocal transport behaviors and first-principles density functional theory calculations. Our methodology paves the way for functional defect engineering that entangles spin and momentum of itinerant electrons for emerging electronic applications.

Pure Spin Currents Driven by Colossal Spin-Orbit Coupling on Two-Dimensional Surface Conducting SrTiO3.

Spin accumulation is generated by passing a charge current through a ferromagnetic layer and sensed by other ferromagnetic layers downstream. Pure spin currents can also be generated in which spin currents flow and are detected as a nonlocal resistance in which the charge current is diverted away from the voltage measurement point. Here, we report nonlocal spin-transport on two-dimensional surface-conducting SrTiO3 (STO) without a ferromagnetic spin-injector via the spin Hall effect (and inverse spin Hall effect). By applying magnetic fields to the Hall bars at different angles to the nonlocal spin-diffusion, we demonstrate an anisotropic spin-signal that is consistent with a Hanle precession of a pure spin current. We extract key transport parameters for surface-conducting STO, including: a spin Hall angle of γ ≈ (0.25 ± 0.05), a spin lifetime of τ ∼ 49 ps, and a spin diffusion length of λs ≈ (1.23 ± 0.7) µm at 2 K.

Catalyst- and Solvent-Free Synthesis of a Chemically Stable Aza-Bridged Bis(phenanthroline) Macrocycle-Linked Covalent Organic Framework.

Developing new linkage-based covalent organic frameworks (COFs) is one of the major topics in reticular chemistry. Electrically conductive COFs have enabled applications in energy storage and electrochemical catalysis, which are not feasible using insulating COFs. Despite significant advances, the construction of chemically stable conductive COFs by the formation of new linkages remains relatively unexplored and challenging. Here we report the solvent- and catalyst-free synthesis of a two-dimensional aza-bridged bis(phenanthroline) macrocycle-linked COF (ABBPM-COF) from the thermally induced poly-condensation of a tri-topic monomer and ammonia gas. The ABBPM-COF structure was elucidated using multiple techniques, including X-ray diffraction analysis combined with structural simulation, revealing its crystalline nature with an ABC stacking mode. Further experiments demonstrated its excellent chemical stability in acid/base solutions. Electrical-conductivity measurements showed that the insulating ABBPM-COF becomes a semiconducting material after exposure to iodine vapor.

Anisotropic Angstrom-Wide Conductive Channels in Black Phosphorus by Top-down Cu Intercalation.

Intercalation in black phosphorus (BP) can induce and modulate a variety of the properties including superconductivity like other two-dimensional (2D) materials. In this perspective, spatially controlled intercalation has the possibility to incorporate different properties into a single crystal of BP. We demonstrate anisotropic angstrom-wide (∼4.3 Å) Cu intercalation in BP, where Cu atoms are intercalated along a zigzag direction of BP because of its inherent anisotropy. With atomic structure, its microstructural effects, arising from the angstrom-wide Cu intercalation, were investigated and extended to relation with macrostructure. As the intercalation mechanism, it was revealed by in situ transmission electron microscopy and theoretical calculation that Cu atoms are intercalated through top-down direction of BP. The Cu intercalation anisotropically induces transition of angstrom-wide electronic channels from semiconductor to semimetal in BP. Our findings throw light on the fundamental relationship between microstructure changes and properties in intercalated BP, and tailoring anisotropic 2D materials at angstrom scale.

A scalable molecule-based magnetic thin film for spin-thermoelectric energy conversion.

Spin thermoelectrics, an emerging thermoelectric technology, offers energy harvesting from waste heat with potential advantages of scalability and energy conversion efficiency, thanks to orthogonal paths for heat and charge flow. However, magnetic insulators previously used for spin thermoelectrics pose challenges for scale-up due to high temperature processing and difficulty in large-area deposition. Here, we introduce a molecule-based magnetic film for spin thermoelectric applications because it entails versatile synthetic routes in addition to weak spin-lattice interaction and low thermal conductivity. Thin films of CrII[CrIII(CN)6], Prussian blue analogue, electrochemically deposited on Cr electrodes at room temperature show effective spin thermoelectricity. Moreover, the ferromagnetic resonance studies exhibit an extremely low Gilbert damping constant ~(2.4 ± 0.67) × 10-4, indicating low loss of heat-generated magnons. The demonstrated STE applications of a new class of magnet will pave the way for versatile recycling of ubiquitous waste heat.

Correction: Suppression of metal-to-insulator transition using strong interfacial coupling at cubic and orthorhombic perovskite oxide heterointerfaces.

Correction for 'Suppression of metal-to-insulator transition using strong interfacial coupling at cubic and orthorhombic perovskite oxide heterointerfaces' by Woonbae Sohn et al., Nanoscale, 2021, 13, 708-715, DOI: 10.1039/D0NR07545K.

Suppression of metal-to-insulator transition using strong interfacial coupling at cubic and orthorhombic perovskite oxide heterointerfaces.

A quasi-two-dimensional electron gas (2DEG) evolved at the LaAlO3 (LAO)/SrTiO3 (STO) interface has attracted significant attention, because the insertion of perovskite titanates can tune the 2DEG conductivity. However, this depends on the Ti-O-Ti bonding angle and structural symmetry. In this study, we controlled the octahedral tilt of the LAO/CaTiO3 (CTO) interface by heterostructuring it with CTO grown on STO substrates of various thicknesses. The 2DEG was maintained when the thickness of CTO was below the critical thickness of 5 unit cells (uc); however, it was suppressed when the CTO thickness was above the critical thickness. High-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) combined with integrated differential phase contrast (iDPC) STEM imaging was used to visualize the TiO6 octahedral tilt propagation and symmetry of the 5 uc and 24 uc CTO films. The symmetry of the 5 uc CTO film resembled that of the STO substrate, whereas the octahedral tilt propagated in the 24 uc CTO film due to the structural relaxation. These results show that the interface engineering of the octahedral tilt can enable or suppress the formation of the 2DEG in perovskite oxides.

Synthesis of a Copper 1,3,5-Triamino-2,4,6-benzenetriol Metal-Organic Framework.

We report the synthesis and characterization of a two-dimensional (2D) MX2Y2-type (M = metal, X, Y = N, S, O, and X ≠ Y) copper 1,3,5-triamino-2,4,6-benzenetriol metal-organic framework (Cu3(TABTO)2-MOF). The role of oxygen in the synthesis of this MOF was investigated. Copper metal is formed along with the MOF when the synthesis is done in argon as suggested by XRD. When the reaction was exposed to air with vigorous stirring, copper metal was not observed by XRD. However, if there is no stirring, then copper metal is formed, and we learned that this is because oxygen was not allowed to enter the solvent due to the formation of a MOF film at the air/water interface. For the sample synthesized in argon (Cu3(TABTO)2-Ar), an insulating Cu3(TABTO)2-Ar pellet (σ < 10-10 S cm-1) became a metallic conductor with an electrical conductivity of 0.78 S cm-1 at 300 K after exposure to iodine vapor. This work provides further insights into the role of oxygen in the synthesis of redox-active ligand-based MOFs, expands the family of 2D redox-active ligand-based electrically conductive MOFs, and offers more opportunities in sensing, photocatalytic, electronic, and energy-related applications.

Reprogrammable Ferromagnetic Domains for Reconfigurable Soft Magnetic Actuators.

Soft magnetic materials have shown promise in diverse applications due to their fast response, remote actuation, and large penetration range for various conditions. Herein, a new soft magnetic composite material capable of reprogramming its magnetization profile without changing intrinsic magnetic properties of embedded magnetic particles or the molecular property of base material is reported. This composite contains magnetic microspheres in an elastomeric matrix, and the magnetic microspheres are composed of ferromagnetic microparticles encapsulated with oligomeric-PEG. By controlling the encapsulating polymer phase transition, the magnetization profiles of the magnetic composite can be rewritten by physically realigning the ferromagnetic particles. Diverse magnetic actuators with reprogrammable magnetization profiles are developed to demonstrate the complete reprogramming of complex magnetization profile.

Observation of spin-polarized Anderson state around charge neutral point in graphene with Fe-clusters.

The pristine graphene described with massless Dirac fermion could bear topological insulator state and ferromagnetism via the band structure engineering with various adatoms and proximity effects from heterostructures. In particular, topological Anderson insulator state was theoretically predicted in tight-binding honeycomb lattice with Anderson disorder term. Here, we introduced physi-absorbed Fe-clusters/adatoms on graphene to impose exchange interaction and random lattice disorder, and we observed Anderson insulator state accompanying with Kondo effect and field-induced conducting state upon applying the magnetic field at around a charge neutral point. Furthermore, the emergence of the double peak of resistivity at ν = 0 state indicates spin-splitted edge state with high effective exchange field (>70 T). These phenomena suggest the appearance of topological Anderson insulator state triggered by the induced exchange field and disorder.

Improved Efficiency of Perovskite Solar Cells Using a Nitrogen-Doped Graphene-Oxide-Treated Tin Oxide Layer.

Tin oxide (SnO2) is widely adopted as an electron transport layer in perovskite solar cells (PeSCs) because it has high electron mobility, excellent charge selective behavior owing to a large band gap of 3.76 eV, and low-temperature processibility. To achieve highly efficient SnO2-based PeSCs, it is necessary to control the oxygen vacancies in the SnO2 layer, since the electrical and optical properties vary depending on the oxidation state of Sn. This study demonstrates that the performance of PeSCs may be improved by using nitrogen-doped graphene oxide (NGO) as an oxidizing agent for SnO2. Since NGO changes the oxidation state of the Sn in SnO2 from Sn2+ to Sn4+, the oxygen vacancies in SnO2 can be reduced using NGO. Multiple devices are fabricated, and various techniques are used to assess their performance, including X-ray photoelectron spectroscopy, dark current analysis, and the dependence of the open-circuit voltage on light intensity. Compared with the average power conversion efficiency (PCE) of control devices, PeSCs with SnO2:NGO composite layers exhibit greater PCEs with less deviation. Therefore, the introduction of NGO in a SnO2 layer can be regarded as an effective method of controlling the oxidation state of SnO2 to improve the performance of PeSCs.

Partial Oxidation-Induced Electrical Conductivity and Paramagnetism in a Ni(II) Tetraaza[14]annulene-Linked Metal Organic Framework.

We report the synthesis and characterization of a two-dimensional (2D) conjugated Ni(II) tetraaza[14]annulene-linked metal organic framework (NiTAA-MOF) where NiTAA is a macrocyclic MN4 (M = metal, N = nitrogen) compound. The structure of NiTAA-MOF was elucidated by Fourier-transform infrared, X-ray photoemission, and X-ray diffraction spectroscopies, in combination with density functional theory (DFT) calculations. When chemically oxidized by iodine, the insulating bulk NiTAA-MOF (σ < 10-10 S/cm) exhibits an electrical conductivity of 0.01 S/cm at 300 K, demonstrating the vital role of ligand oxidation in the electrical conductivity of 2D MOFs. Magnetization measurements show that iodine-doped NiTAA-MOF is paramagnetic with weak antiferromagnetic coupling due to the presence of organic radicals of oxidized ligands and high-spin Ni(II) sites of the missing-linker defects. In addition to providing further insights into the origin of the induced electrical conductivity in 2D MOFs, both pristine and iodine-doped NiTAA-MOF synthesized in this work could find potential applications in areas such as catalase mimics, catalysis, energy storage, and dynamic nuclear polarization-nuclear magnetic resonance (DNP-NMR).