Temperature Dependence of Relativistic Valence Band Splitting Induced by an Altermagnetic Phase Transition.

Altermagnetic (AM) materials exhibit non-relativistic, momentum-dependent spin-split states, ushering in new opportunities for spin electronic devices. While the characteristics of spin-splitting are documented within the framework of the non-relativistic spin group symmetry, there is limited exploration of the inclusion of relativistic symmetry and its impact on the emergence of a novel spin-splitting in the band structure. This study delves into the intricate relativistic electronic structure of an AM material, α-MnTe. Employing temperature-dependent angle-resolved photoelectron spectroscopy across the AM phase transition, the emergence of a relativistic valence band splitting concurrent with the establishment of magnetic order is elucidated. This discovery is validated through disordered local moment calculations, modeling the influence of magnetic order on the electronic structure and confirming the magnetic origin of the observed splitting. The temperature-dependent splitting is ascribed to the advent of relativistic spin-splitting resulting from the strengthening of AM order in α-MnTe as the temperature decreases. This sheds light on a previously unexplored facet of this intriguing material.

Biosynthesis of ternary NiCoFe2O4 nanoflowers: investigating their 3D structure and potential use in gene delivery.

Multicomponent nanoparticle systems are known for their varied properties and functions, and have shown potential as gene nanocarriers. This study aims to synthesize and characterize ternary nickel-cobalt-ferrite (NiCoFe2O4) nanoparticles with the potential to serve as gene nanocarriers for cancer/gene therapy. The biogenic nanocarriers were prepared using a simple and eco-friendly method following green chemistry principles. The physicochemical properties of the nanoparticles were analyzed by X-ray diffraction, vibrating sample magnetometer, X-ray photoelectron spectroscopy, and Brunauer-Emmett-Teller. To evaluate the morphology of the nanoparticles, the field emission scanning electron microscopy with energy dispersive X-Ray spectroscopy, high-resolution transmission electron microscopy imaging, and electron tomography were conducted. Results indicate the nanoparticles have a nanoflower morphology with a mesoporous nature and a cubic spinel structure, where the rod and spherical nanoparticles became rose-like with a specific orientation. These nanoparticles were found to have minimal toxicity in human embryonic kidney 293 (HEK-293 T) cells at concentrations of 1 to 250 µg·mL-1. We also demonstrated that the nanoparticles could be used as gene nanocarriers for delivering genes to HEK-293 T cells using an external magnetic field, with optimal transfection efficiency achieved at an N/P ratio of 2.5. The study suggests that biogenic multicomponent nanocarriers show potential for safe and efficient gene delivery in cancer/gene therapy.

Carboxymethyl starch as a reducing and capping agent in the hydrothermal synthesis of selenium nanostructures for use with three-dimensional-printed hydrogel carriers.

The hydrothermal method is a cost-effective and eco-friendly route for preparing various nanomaterials. It can use a capping agent, such as a polysaccharide, to govern and define the nanoparticle morphology. Elemental selenium nanostructures (spheres and rods) were synthesized and stabilized using a tailor-made carboxymethyl starch (CMS, degree of substitution = 0.3) under hydrothermal conditions. CMS is particularly convenient because it acts simultaneously as the capping and reducing agent, as verified by several analytical techniques, while the reaction relies entirely on green solvents. Furthermore, the effect of sodium selenite concentration, reaction time and temperature on the nanoparticle size, morphology, microstructure and chemical composition was investigated to identify the ideal synthesis conditions. A pilot experiment demonstrated the feasibility of implementing the synthesized nanoparticles into vat photopolymerization three-dimensional-printed hydrogel carriers based on 2-hydroxyethyl methacrylate (HEMA). When submersed into the water, the subsequent particle release was confirmed by dynamic light scattering (DLS), promising great potential for use in bio-three-dimensional printing and other biomedical applications.

Atomically sharp domain walls in an antiferromagnet.

The interest in understanding scaling limits of magnetic textures such as domain walls spans the entire field of magnetism from its physical fundamentals to applications in information technologies. Here, we explore antiferromagnetic CuMnAs in which imaging by x-ray photoemission reveals the presence of magnetic textures down to nanoscale, reaching the detection limit of this established microscopy in antiferromagnets. We achieve atomic resolution by using differential phase-contrast imaging within aberration-corrected scanning transmission electron microscopy. We identify abrupt domain walls in the antiferromagnetic film corresponding to the Néel order reversal between two neighboring atomic planes. Our work stimulates research of magnetic textures at the ultimate atomic scale and sheds light on electrical and ultrafast optical antiferromagnetic devices with magnetic field-insensitive neuromorphic functionalities.

Defect-driven antiferromagnetic domain walls in CuMnAs films.

Efficient manipulation of antiferromagnetic (AF) domains and domain walls has opened up new avenues of research towards ultrafast, high-density spintronic devices. AF domain structures are known to be sensitive to magnetoelastic effects, but the microscopic interplay of crystalline defects, strain and magnetic ordering remains largely unknown. Here, we reveal, using photoemission electron microscopy combined with scanning X-ray diffraction imaging and micromagnetic simulations, that the AF domain structure in CuMnAs thin films is dominated by nanoscale structural twin defects. We demonstrate that microtwin defects, which develop across the entire thickness of the film and terminate on the surface as characteristic lines, determine the location and orientation of 180∘ and 90∘ domain walls. The results emphasize the crucial role of nanoscale crystalline defects in determining the AF domains and domain walls, and provide a route to optimizing device performance.

Hierarchical Atomic Layer Deposited V2 O5 on 3D Printed Nanocarbon Electrodes for High-Performance Aqueous Zinc-Ion Batteries.

Aqueous rechargeable zinc-ion batteries (ARZIBs) are promising energy storage systems owing to their ecofriendliness, safety, and cost-efficiency. However, the sluggish Zn2+ diffusion kinetics originated from its inherent large atomic mass and high polarization remains an ongoing challenge. To this end, electrodes with 3D architectures and high porosity are highly desired. This work reports a rational design and fabrication of hierarchical core-shell structured cathodes (3D@V2 O5 ) for ARZIBs by integrating fused deposition modeling (FDM) 3D-printing with atomic layer deposition (ALD). The 3D-printed porous carbon network provides an entangled electron conductive core and interconnected ion diffusion channels, whereas ALD-coated V2 O5 serves as an active shell without sacrificing the porosity for facilitated Zn2+ diffusion. This endows the 3D@V2 O5 cathode with high specific capacity (425 mAh g-1 at 0.3 A g-1 ), competitive energy and power densities (316 Wh Kg-1 at 213 W kg-1 and 163 Wh Kg-1 at 3400 W kg-1 ), and good rate performance (221 mAh g-1 at 4.8 A g-1 ). The developed 3D@V2 O5 cathode provides a promising model for customized and scalable battery electrode engineering technology. As the ALD-coated layer determines the functional properties, the proposed strategy shows a promising prospect of FDM 3D printing using 1D carbon materials for future energy storage.

Microwave plasma-based high temperature dehydrogenation of hydrocarbons and alcohols as a single route to highly efficient gas phase synthesis of freestanding graphene.

Understanding underlying processes behind the simple and easily scalable graphene synthesis methods enables their large-scale deployment in the emerging energy storage and printable device applications. Microwave plasma decomposition of organic precursors forms a high-temperature environment, above 3000 K, where the process of catalyst-free dehydrogenation and consequent formation of C2molecules leads to nucleation and growth of high-quality few-layer graphene (FLG). In this work, we show experimental evidence that a high-temperature environment with a gas mixture of H2and acetylene, C2H2, leads to a transition from amorphous to highly crystalline material proving the suggested dehydrogenation mechanism. The overall conversion efficiency of carbon to FLG reached up to 47%, three times as much as for methane or ethanol, and increased with increasing microwave power (i.e. with the size of the high-temperature zone) and hydrocarbon flow rate. The yield decreased with decreasing C:H ratio while the best quality FLG (low D/G-0.5 and high 2D/G-1.5 Raman band ratio) was achieved for C:H ratio of 1:3. The structures contained less than 1 at% of oxygen. No additional hydrogen was necessary for the synthesis of FLG from higher alcohols having the same stoichiometry, 1-propanol and isopropanol, but the yield was lower, 15%, and dependent on the atom arrangement of the precursor. The prepared FLG nanopowder was analyzed by scanning electron microscopy, Raman, x-ray photoelectron spectroscopy, and thermogravimetry. Microwave plasma was monitored by optical emission spectroscopy.

Mn-Rich MnSb2 Te4 : A Topological Insulator with Magnetic Gap Closing at High Curie Temperatures of 45-50 K.

Ferromagnetic topological insulators exhibit the quantum anomalous Hall effect, which is potentially useful for high-precision metrology, edge channel spintronics, and topological qubits.  The stable 2+ state of Mn enables intrinsic magnetic topological insulators. MnBi2 Te4 is, however, antiferromagnetic with 25 K Néel temperature and is strongly n-doped. In this work, p-type MnSb2 Te4 , previously considered topologically trivial, is shown to be a ferromagnetic topological insulator for a few percent Mn excess. i) Ferromagnetic hysteresis with record Curie temperature of 45-50 K, ii) out-of-plane magnetic anisotropy, iii) a 2D Dirac cone with the Dirac point close to the Fermi level, iv) out-of-plane spin polarization as revealed by photoelectron spectroscopy, and v) a magnetically induced bandgap closing at the Curie temperature, demonstrated by scanning tunneling spectroscopy (STS), are shown. Moreover, a critical exponent of the magnetization ß ≈ 1 is found, indicating the vicinity of a quantum critical point. Ab initio calculations reveal that Mn-Sb site exchange provides the ferromagnetic interlayer coupling and the slight excess of Mn nearly doubles the Curie temperature. Remaining deviations from the ferromagnetic order open the inverted bulk bandgap and render MnSb2 Te4 a robust topological insulator and new benchmark for magnetic topological insulators.

Rhenium Doping of Layered Transition-Metal Diselenides Triggers Enhancement of Photoelectrochemical Activity.

The ever decreasing sources of fossil fuels have launched extensive research of alternative materials that might play a key role in their replacement. Therefore, the scientific community continuously investigates the possibilities of maximizing the working capacity of such materials in order to fulfill energy challenges in the near future. In this context, doping of the semiconducting materials is a versatile strategy to trigger their physicochemical properties as well their electrochemical performance. Herein, the impact of rhenium doping toward photoelectrochemical activity of MoSe2 and WSe2 was studied. Our results indicate that rhenium as a dopant contributes to better overall electrochemical performance, that is, an easier electron transfer of these materials compared to pristine compounds. Additionally, the photoelectrochemical measurements revealed that the doping with rhenium generated an enhancement of the photocurrent response of MoSe2 as well as WSe2 under UV light illumination.

Atomic Layer Deposition of Electrocatalytic Insulator Al2O3 on Three-Dimensional Printed Nanocarbons.

The advantages of three-dimensional (3D) printing technologies, such as rapid-prototyping and the freedom to customize electrodes in any design, have elevated the benchmark of conventional electrochemical studies. Furthermore, the 3D printed electrodes conveniently accommodate other active layers for diverse applications such as energy storage, catalysis, and sensors. Nevertheless, to enhance a complex 3D structure while preserving the fine morphology, conformal deposition by atomic layer deposition (ALD) technique is a powerful solution. Herein, we present the concept of coating Al2O3 by ALD with different thicknesses from 20 to 120 cycles on the 3D printed nanocarbon/PLA electrodes for the electrocatalytic oxidation of catechol as an important biomarker. Overall, 80 ALD cycle Al2O3 achieved an optimum thickness for catechol electrocatalysis. This is resonated with the enhanced adsorption of catechol at the electrode surface and efficient electron transfer, according to the two-proton, two-electron-transfer mechanism, as well as for the passivation of surface defects of the nanocarbon electrode. This work compellingly demonstrates the prospect of 3D printed electrodes modified by a functional layer utilizing a low-temperature ALD process that can be extended to other arbitrary surfaces.

Atomic Layer Deposition of SnO2-Coated Anodic One-Dimensional TiO2 Nanotube Layers for Low Concentration NO2 Sensing.

The continuous emission of nitrous oxides contributes to the overall air pollution and deterioration of air quality. In particular, an effective NO2 sensor capable of low concentration detection for continuous monitoring is demanded for safety, health, and wellbeing. The sensing performance of a metal oxide-based sensor is predominantly influenced by the availability of surface area for O2 adsorption and desorption, efficient charge transport, and size or thickness of the sensing layer. In this study, we utilized anodic one-dimensional (1D) TiO2 nanotube layers of 5 µm thick which offer large surface area and unidirectional electron transport pathway as a platform to accommodate thin SnO2 coatings as a sensing layer. Conformal and homogeneous SnO2 coatings across the entire inner and outer TiO2 nanotubes were achieved by atomic layer deposition with a controlled thickness of 4, 8, and 16 nm. The SnO2-coated TiO2 nanotube layers attained a higher sensing response than a reference Figaro SnO2 sensor. Specifically, the 8 nm SnO2-coated TiO2 nanotube layer has recorded up to ten-fold enhancement in response as compared to the blank nanotubes for the detection of 1 ppm NO2 at an operating temperature of 300 °C with 0.5 V applied bias. This is attributed to the SnO2/TiO2 heterojunction effect and controlled SnO2 thickness within the range of the Debye length. We demonstrated in this work, a tailored large surface area platform based on 1D nanotubes with thin active coatings as an efficient approach for sensing applications and beyond.

TiO2 Nanotube Layers Decorated with Al2O3/MoS2/Al2O3 as Anode for Li-ion Microbatteries with Enhanced Cycling Stability.

TiO2 nanotube layers (TNTs) decorated with Al2O3/MoS2/Al2O3 are investigated as a negative electrode for 3D Li-ion microbatteries. Homogenous nanosheets decoration of MoS2, sandwiched between Al2O3 coatings within self-supporting TNTs was carried out using atomic layer deposition (ALD) process. The structure, morphology, and electrochemical performance of the Al2O3/MoS2/Al2O3-decorated TNTs were studied using scanning transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and chronopotentiometry. Al2O3/MoS2/Al2O3-decorated TNTs deliver an areal capacity almost three times higher than that obtained for MoS2-decorated TNTs and as-prepared TNTs after 100 cycles at 1C. Moreover, stable and high discharge capacity (414 µAh cm-2) has been obtained after 200 cycles even at very fast kinetics (3C).

Laser-induced crystallization of anodic TiO2 nanotube layers.

In this study, crystallization of amorphous TiO2 nanotube (TNT) layers upon optimized laser annealing is shown. The resulting anatase TNT layers do not show any signs of deformation or melting. The crystallinity of the laser annealed TNT layers was investigated using X-ray diffraction, Raman spectroscopy, and high-resolution transmission electron microscopy (HRTEM). The study of the (photo-)electrochemical properties showed that the laser annealed TNT layers were more defective than conventional TNT layers annealed in a muffle oven at 400 °C, resulting in a higher charge recombination rate and lower photocurrent response. However, a lower overpotential for hydrogen evolution reaction was observed for the laser annealed TNT layer compared to the oven annealed TNT layer.

2D MoS2 nanosheets on 1D anodic TiO2 nanotube layers: an efficient co-catalyst for liquid and gas phase photocatalysis.

One-dimensional TiO2 nanotube layers with different dimensions were homogeneously decorated with 2D MoS2 nanosheets via atomic layer deposition and employed for liquid and gas phase photocatalysis. The 2D MoS2 nanosheets revealed a high amount of exposed active edge sites and strongly enhanced the photocatalytic performance of TiO2 nanotube layers.

Generation and Stabilization of Small Platinum Clusters Pt12±x Inside a Metal-Organic Framework.

The generation and matrix stabilization of ligand-free, small platinum nanoclusters (NCs) Pt12±x is presented. The metal-organic framework-template approach is based on encapsulating CO-ligated, atom-precise Pt9 Chini clusters [{Pt3(CO)6}3]2- into the zeolitic imidazolate framework ZIF-8. The selective formation of the air-stable inclusion compound [NBu4]2[{Pt3(CO)6}4]@ZIF-8 of defined atomicity Pt12 and with Pt loadings of 1-20 wt % was monitored by UV/vis and IR spectroscopy and was confirmed by high-resolution transmission electron microscopy (HR-TEM), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), X-ray photoelectron spectroscopy (XPS), and powder X-ray diffraction (PXRD). Thermally induced decarbonylation at 200 °C yields the composite material Ptn@ZIF-8 with a cluster atomicity n close to 12, irrespective of the Pt loading. The PtNCs retain their size even during annealing at 300 °C for 24 h and during catalytic hydrogenation of 1-hexene at 25 °C in the liquid phase. The Ptn@ZIF-8 material can conveniently be used for storing small PtNCs and their further processing. Removal of the protective ZIF-8 matrix under acidic conditions and transfer of the PtNCs to carbon substrates yields defined aggregation to small Pt nanoparticles (1.14 ± 0.35 nm, HR-TEM), which have previously shown exceptional performance in the electrocatalytic oxygen reduction reaction (ORR).

Optimizing the Size of Platinum Nanoparticles for Enhanced Mass Activity in the Electrochemical Oxygen Reduction Reaction.

High oxygen reduction (ORR) activity has been for many years considered as the key to many energy applications. Herein, by combining theory and experiment we prepare Pt nanoparticles with optimal size for the efficient ORR in proton-exchange-membrane fuel cells. Optimal nanoparticle sizes are predicted near 1, 2, and 3 nm by computational screening. To corroborate our computational results, we have addressed the challenge of approximately 1 nm sized Pt nanoparticle synthesis with a metal-organic framework (MOF) template approach. The electrocatalyst was characterized by HR-TEM, XPS, and its ORR activity was measured using a rotating disk electrode setup. The observed mass activities (0.87±0.14 A mgPt -1 ) are close to the computational prediction (0.99 A mgPt -1 ). We report the highest to date mass activity among pure Pt catalysts for the ORR within similar size range. The specific and mass activities are twice as high as the Tanaka commercial Pt/C catalysis.

Bismuth Oxychloride Nanoplatelets by Breakdown Anodization.

Herein, the synthesis of BiOCl nanoplatelets of various dimensions is demonstrated. These materials were prepared by anodic oxidation of Bi ingots in diluted HCl under dielectric breakdown conditions, triggered by a sufficiently high anodic field. Additionally, it is shown that the use of several other common diluted acids (HNO3, H2SO4, lactic acid) resulted in the formation of various different nanostructures. The addition of NH4F to the acidic electrolytes accelerated the growth rate resulting in bismuth-based nanostructures with comparably smaller dimensions and an enormous volume expansion observed during the growth. On the other hand, the addition of lactic acid to the acidic electrolytes decelerated the oxide growth rate. The resulting nanostructures were characterized using SEM, XRD and TEM. BiOCl nanoplatelets received by anodization in 1 M HCl were successfully employed for the photocatalytic decomposition of methylene blue dye and showed a superior performance compared to commercially available BiOCl powder with a similar crystalline structure, confirming its potential as a visible light photocatalyst.

Top-Down Synthesis of Nanostructured Platinum-Lanthanide Alloy Oxygen Reduction Reaction Catalysts: Pt xPr/C as an Example.

The oxygen reduction reaction (ORR) is of great interest for future sustainable energy conversion and storage, especially concerning fuel cell applications. The preparation of active, affordable, and scalable electrocatalysts and their application in fuel cell engines of hydrogen cars is a prominent step toward the reduction of air pollution, especially in urban areas. Alloying nanostructured Pt with lanthanides is a promising approach to enhance its catalytic ORR activity, whereby the development of a simple synthetic route turned out to be a nontrivial endeavor. Herein, for the first time, we present a successful single-step, scalable top-down synthetic route for Pt-lanthanide alloy nanoparticles, as witnessed by the example of Pr-alloyed Pt nanoparticles. The catalyst was characterized by high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffraction, and photoelectron spectroscopy, and its electrocatalytic oxygen reduction activity was investigated using a rotating disk electrode technique. Pt xPr/C showed ∼3.5 times higher [1.96 mA/cm2Pt, 0.9 V vs reversible hydrogen electrode (RHE)] specific activity and ∼1.7 times higher (0.7 A/mgPt, 0.9 V vs RHE) mass activity compared to commercial Pt/C catalysts. On the basis of previous findings and characterization of the Pt xPr/C catalyst, the activity improvement over commercial Pt/C originates from a lattice strain introduced by the alloying process.

Mitigating Curtaining Artifacts During Ga FIB TEM Lamella Preparation of a 14 nm FinFET Device.

We report on the mitigation of curtaining artifacts during transmission electron microscopy (TEM) lamella preparation by means of a modified ion beam milling approach, which involves altering the incident angle of the Ga ions by rocking of the sample on a special stage. We applied this technique to TEM sample preparation of a state-of-the-art integrated circuit based on a 14-nm technology node. Site-specific lamellae with a thickness <15 nm were prepared by top-down Ga focused ion beam polishing through upper metal contacts. The lamellae were analyzed by means of high-resolution TEM, which showed a clear transistor structure and confirmed minimal curtaining artifacts. The results are compared with a standard inverted thinning preparation technique.