Chemical short-range disorder in lithium oxide cathodes.

Ordered layered structures serve as essential components in lithium (Li)-ion cathodes1-3. However, on charging, the inherently delicate Li-deficient frameworks become vulnerable to lattice strain and structural and/or chemo-mechanical degradation, resulting in rapid capacity deterioration and thus short battery life2,4. Here we report an approach that addresses these issues using the integration of chemical short-range disorder (CSRD) into oxide cathodes, which involves the localized distribution of elements in a crystalline lattice over spatial dimensions, spanning a few nearest-neighbour spacings. This is guided by fundamental principles of structural chemistry and achieved through an improved ceramic synthesis process. To demonstrate its viability, we showcase how the introduction of CSRD substantially affects the crystal structure of layered Li cobalt oxide cathodes. This is manifested in the transition metal environment and its interactions with oxygen, effectively preventing detrimental sliding of crystal slabs and structural deterioration during Li removal. Meanwhile, it affects the electronic structure, leading to improved electronic conductivity. These attributes are highly beneficial for Li-ion storage capabilities, markedly improving cycle life and rate capability. Moreover, we find that CSRD can be introduced in additional layered oxide materials through improved chemical co-doping, further illustrating its potential to enhance structural and electrochemical stability. These findings open up new avenues for the design of oxide cathodes, offering insights into the effects of CSRD on the crystal and electronic structure of advanced functional materials.

Bevel-edge epitaxy of ferroelectric rhombohedral boron nitride single crystal.

Within the family of two-dimensional dielectrics, rhombohedral boron nitride (rBN) is considerably promising owing to having not only the superior properties of hexagonal boron nitride1-4-including low permittivity and dissipation, strong electrical insulation, good chemical stability, high thermal conductivity and atomic flatness without dangling bonds-but also useful optical nonlinearity and interfacial ferroelectricity originating from the broken in-plane and out-of-plane centrosymmetry5-23. However, the preparation of large-sized single-crystal rBN layers remains a challenge24-26, owing to the requisite unprecedented growth controls to coordinate the lattice orientation of each layer and the sliding vector of every interface. Here we report a facile methodology using bevel-edge epitaxy to prepare centimetre-sized single-crystal rBN layers with exact interlayer ABC stacking on a vicinal nickel surface. We realized successful accurate fabrication over a single-crystal nickel substrate with bunched step edges of the terrace facet (100) at the bevel facet (110), which simultaneously guided the consistent boron-nitrogen bond orientation in each BN layer and the rhombohedral stacking of BN layers via nucleation near each bevel facet. The pure rhombohedral phase of the as-grown BN layers was verified, and consequently showed robust, homogeneous and switchable ferroelectricity with a high Curie temperature. Our work provides an effective route for accurate stacking-controlled growth of single-crystal two-dimensional layers and presents a foundation for applicable multifunctional devices based on stacked two-dimensional materials.

Tracking cubic ice at molecular resolution.

Ice is present everywhere on Earth and has an essential role in several areas, such as cloud physics, climate change and cryopreservation. The role of ice is determined by its formation behaviour and associated structure. However, these are not fully understood1. In particular, there is a long-standing debate about whether water can freeze to form cubic ice-a currently undescribed phase in the phase space of ordinary hexagonal ice2-6. The mainstream view inferred from a collection of laboratory data attributes this divergence to the inability to discern cubic ice from stacking-disordered ice-a mixture of cubic and hexagonal sequences7-11. Using cryogenic transmission electron microscopy combined with low-dose imaging, we show here the preferential nucleation of cubic ice at low-temperature interfaces, resulting in two types of separate crystallization of cubic ice and hexagonal ice from water vapour deposition at 102 K. Moreover, we identify a series of cubic-ice defects, including two types of stacking disorder, revealing the structure evolution dynamics supported by molecular dynamics simulations. The realization of direct, real-space imaging of ice formation and its dynamic behaviour at the molecular level provides an opportunity for ice research at the molecular level using transmission electron microscopy, which may be extended to other hydrogen-bonding crystals.

Disorder-tuned conductivity in amorphous monolayer carbon.

Correlating atomic configurations-specifically, degree of disorder (DOD)-of an amorphous solid with properties is a long-standing riddle in materials science and condensed matter physics, owing to difficulties in determining precise atomic positions in 3D structures1-5. To this end, 2D systems provide insight to the puzzle by allowing straightforward imaging of all atoms6,7. Direct imaging of amorphous monolayer carbon (AMC) grown by laser-assisted depositions has resolved atomic configurations, supporting the modern crystallite view of vitreous solids over random network theory8. Nevertheless, a causal link between atomic-scale structures and macroscopic properties remains elusive. Here we report facile tuning of DOD and electrical conductivity in AMC films by varying growth temperatures. Specifically, the pyrolysis threshold temperature is the key to growing variable-range-hopping conductive AMC with medium-range order (MRO), whereas increasing the temperature by 25 °C results in AMC losing MRO and becoming electrically insulating, with an increase in sheet resistance of 109 times. Beyond visualizing highly distorted nanocrystallites embedded in a continuous random network, atomic-resolution electron microscopy shows the absence/presence of MRO and temperature-dependent densities of nanocrystallites, two order parameters proposed to fully describe DOD. Numerical calculations establish the conductivity diagram as a function of these two parameters, directly linking microstructures to electrical properties. Our work represents an important step towards understanding the structure-property relationship of amorphous materials at the fundamental level and paves the way to electronic devices using 2D amorphous materials.

Seeded growth of large single-crystal copper foils with high-index facets.

The production of large single-crystal metal foils with various facet indices has long been a pursuit in materials science owing to their potential applications in crystal epitaxy, catalysis, electronics and thermal engineering1-5. For a given metal, there are only three sets of low-index facets ({100}, {110} and {111}). In comparison, high-index facets are in principle infinite and could afford richer surface structures and properties. However, the controlled preparation of single-crystal foils with high-index facets is challenging, because they are neither thermodynamically6,7 nor kinetically3 favourable compared to low-index facets6-18. Here we report a seeded growth technique for building a library of single-crystal copper foils with sizes of about 30 × 20 square centimetres and more than 30 kinds of facet. A mild pre-oxidation of polycrystalline copper foils, followed by annealing in a reducing atmosphere, leads to the growth of high-index copper facets that cover almost the entire foil and have the potential of growing to lengths of several metres. The creation of oxide surface layers on our foils means that surface energy minimization is not a key determinant of facet selection for growth, as is usually the case. Instead, facet selection is dictated randomly by the facet of the largest grain (irrespective of its surface energy), which consumes smaller grains and eliminates grain boundaries. Our high-index foils can be used as seeds for the growth of other Cu foils along either the in-plane or the out-of-plane direction. We show that this technique is also applicable to the growth of high-index single-crystal nickel foils, and we explore the possibility of using our high-index copper foils as substrates for the epitaxial growth of two-dimensional materials. Other applications are expected in selective catalysis, low-impedance electrical conduction and heat dissipation.

Dislocation-tuned ferroelectricity and ferromagnetism of the BiFeO3/SrRuO3 interface.

Misfit dislocations at a heteroepitaxial interface produce huge strain and, thus, have a significant impact on the properties of the interface. Here, we use scanning transmission electron microscopy to demonstrate a quantitative unit-cell-by-unit-cell mapping of the lattice parameters and octahedral rotations around misfit dislocations at the BiFeO3/SrRuO3 interface. We find that huge strain field is achieved near dislocations, i.e., above 5% within the first three unit cells of the core, which is typically larger than that achieved from the regular epitaxy thin-film approach, thus significantly altering the magnitude and direction of the local ferroelectric dipole in BiFeO3 and magnetic moments in SrRuO3 near the interface. The strain field and, thus, the structural distortion can be further tuned by the dislocation type. Our atomic-scale study helps us to understand the effects of dislocations in this ferroelectricity/ferromagnetism heterostructure. Such defect engineering allows us to tune the local ferroelectric and ferromagnetic order parameters and the interface electromagnetic coupling, providing new opportunities to design nanosized electronic and spintronic devices.

Epitaxial growth of a 100-square-centimetre single-crystal hexagonal boron nitride monolayer on copper.

The development of two-dimensional (2D) materials has opened up possibilities for their application in electronics, optoelectronics and photovoltaics, because they can provide devices with smaller size, higher speed and additional functionalities compared with conventional silicon-based devices1. The ability to grow large, high-quality single crystals for 2D components-that is, conductors, semiconductors and insulators-is essential for the industrial application of 2D devices2-4. Atom-layered hexagonal boron nitride (hBN), with its excellent stability, flat surface and large bandgap, has been reported to be the best 2D insulator5-12. However, the size of 2D hBN single crystals is typically limited to less than one millimetre13-18, mainly because of difficulties in the growth of such crystals; these include excessive nucleation, which precludes growth from a single nucleus to large single crystals, and the threefold symmetry of the hBN lattice, which leads to antiparallel domains and twin boundaries on most substrates19. Here we report the epitaxial growth of a 100-square-centimetre single-crystal hBN monolayer on a low-symmetry Cu (110) vicinal surface, obtained by annealing an industrial copper foil. Structural characterizations and theoretical calculations indicate that epitaxial growth was achieved by the coupling of Cu <211> step edges with hBN zigzag edges, which breaks the equivalence of antiparallel hBN domains, enabling unidirectional domain alignment better than 99 per cent. The growth kinetics, unidirectional alignment and seamless stitching of the hBN domains are unambiguously demonstrated using centimetre- to atomic-scale characterization techniques. Our findings are expected to facilitate the wide application of 2D devices and lead to the epitaxial growth of broad non-centrosymmetric 2D materials, such as various transition-metal dichalcogenides20-23, to produce large single crystals.

Programmable Ferroelectricity in Hf0.5Zr0.5O2 Enabled by Oxygen Defect Engineering.

Ferroelectricity, especially the Si-compatible type recently observed in hafnia-based materials, is technologically useful for modern memory and logic applications, but it is challenging to differentiate intrinsic ferroelectric polarization from the polar phase and oxygen vacancy. Here, we report electrically controllable ferroelectricity in a Hf0.5Zr0.5O2-based heterostructure with Sr-doped LaMnO3, a mixed ionic-electronic conductor, as an electrode. Electrically reversible extraction and insertion of an oxygen vacancy into Hf0.5Zr0.5O2 are macroscopically characterized and atomically imaged in situ. Utilizing this reversible process, we achieved multilevel polarization states modulated by the electric field. Our study demonstrates the usefulness of the mixed conductor to repair, create, manipulate, and utilize advanced ferroelectric functionality. Furthermore, the programmed ferroelectric heterostructures with Si-compatible doped hafnia are desirable for the development of future ferroelectric electronics.

Ferroelectricity in Epitaxial Perovskite Oxide Bi2WO6 Films with One-Unit-Cell Thickness.

Retaining ferroelectricity in ultrathin films or nanostructures is crucial for miniaturizing ferroelectric devices, but it is a challenging task due to intrinsic depolarization and size effects. In this study, we have shown that it is possible to stably maintain in-plane polarization in an extremely thin, one-unit-cell thick epitaxial Bi2WO6 film. The use of a perfectly lattice-matched NdGaO3 (110) substrate for the Bi2WO6 film minimizes strain and enhances stability. We attribute the residual polarization in this ultrathin film to the crystal stability of the Bi-O octahedral framework against structural distortions. Our findings suggest that ferroelectricity can surpass the critical thickness limit through proper strain engineering, and the Bi2WO6/NdGaO3 (110) system presents a potential platform for designing low-energy consumption, nonvolatile ferroelectric memories.

Scaling of MoS2 Transistors and Inverters to Sub-10 nm Channel Length with High Performance.

Two-dimensional (2D) semiconductors such as monolayer molybdenum disulfide (MoS2) are promising building blocks for ultrascaled field effect transistors (FETs), benefiting from their atomic thickness, dangling-bond-free flat surface, and excellent gate controllability. However, despite great prospects, the fabrication of 2D ultrashort channel FETs with high performance and uniformity remains a challenge. Here, we report a self-encapsulated heterostructure undercut technique for the fabrication of sub-10 nm channel length MoS2 FETs. The fabricated 9 nm channel MoS2 FETs exhibit superior performances compared with sub-15 nm channel length including the competitive on-state current density of 734/433 µA/µm at VDS = 2/1 V, record-low DIBL of ∼50 mV/V, and superior on/off ratio of 3 × 107 and low subthreshold swing of ∼100 mV/dec. Furthermore, the ultrashort channel MoS2 FETs fabricated by this new technique show excellent homogeneity. Thanks to this, we scale the monolayer inverter down to sub-10 nm channel length.

Fermented tea leave extract against oxidative stress and ageing of skin in vitro and in vivo.

OBJECTIVE: The objective is to develop a natural and stable anti-oxidative stress and anti-ageing ingredient. In this study, we evaluated the changes in white tea leaves fermented with Eurotium cristatum PLT-PE and Saccharomyces boulardii PLT-HZ and their efficacy against skin oxidative stress. METHODS: We employed untargeted metabolomics technology to analyse the differential metabolites between tea extract (TE) and fermented tea extract (FTE). In vitro, using H2O2-induced HaCaT cells, we evaluated cell vitality, ROS, and inflammatory factors (TNF-α, IL-1ß, and IL-6). Additionally, we verified the effects on the extracellular matrix and nuclear DNA using fibroblasts or reconstructed skin models. We measured skin hydration, elasticity, wrinkle area, wrinkle area ratio, erythema area, and erythema area ratio in volunteers after using an emulsion containing 3% FTE for 28 and 56 days. RESULTS: Targeted metabolomics analysis of white tea leaves yielded more than 20 differential metabolites with antioxidant and anti-inflammatory activities, including amino acids, polypeptides, quercetin, and liquiritin post-fermentation. FTE, compared to TE, can significantly reduce reactive oxygen species (ROS) and protect against oxidative stress-induced skin damage in H2O2-induced HaCaT cells. FTE can inhibit H2O2-induced collagen degradation by suppressing the MAPK/c-Jun signalling pathway and can also mitigate the reactive oxygen species damage to nuclear DNA. Clinical studies showed that the volunteers' stratum corneum water content, skin elasticity, wrinkle area, wrinkle area ratio, erythema area, and erythema area ratio significantly improved from the baseline after 28 and 56 days of FTE use. CONCLUSION: This study contributes to the growing body of literature supporting the protective effects against skin oxidative stress and ageing from fermented plant extracts. Moreover, our findings might inspire multidisciplinary efforts to investigate new fermentation techniques that could produce even more potent anti-ageing solutions.

OBJECTIF: L'objectif est de développer un ingrédient naturel et stable contre le stress oxydatif et anti­âge. Dans cette étude, nous avons évalué les modifications dans les feuilles de thé blanc fermentées avec la PLT­PE Eurotium cristatum et la PLT­HZ Saccharomyces boulardii et leur efficacité contre le stress oxydatif cutané. MÉTHODES: Nous avons utilisé une technologie de métabolomique non ciblée pour analyser les métabolites différentiels entre l'extrait de thé (ET) et l'extrait de thé fermenté (ETF). In vitro, à l'aide de cellules HaCaT induites par l'H2O2, nous avons évalué la vitalité cellulaire, les ERO et les facteurs inflammatoires (TNF­α, IL­1ß, and IL­6). Nous avons également vérifié les effets sur la matrice extracellulaire et l'ADN nucléaire à l'aide de fibroblastes ou de modèles cutanés reconstruits. Nous avons mesuré l'hydratation de la peau, l'élasticité, la surface de rides, le rapport des surfaces de rides, la surface d'érythème, et le rapport des surfaces d'érythème chez des volontaires ayant utilisé une émulsion contenant 3% d'ETF pendant 28 et 56 jours. RÉSULTATS: L'analyse métabolomique ciblée des feuilles de thé blanc a révélé plus de 20 métabolites différentiels ayant des activités antioxydantes et anti­inflammatoires, notamment des acides aminés, des polypeptides, de la quercétine et de la liquiritine après fermentation. Par rapport à l'ET, l'ETF peut réduire significativement les espèces réactives de l'oxygène (ERO) et protéger contre les lésions cutanées induites par le stress oxydatif dans les cellules HaCaT induites par l'H2O2. L'ETF peut inhiber la dégradation du collagène induite par l'H2O2 en supprimant la voie de signalization MAPK/c­Jun et peut également atténuer les dommages causés par les espèces réactives de l'oxygène à l'ADN nucléaire. Les études cliniques ont montré que la teneur en eau de la couche cornée des volontaires, l'élasticité de la peau, la surface de rides, le rapport des surfaces de rides, la surface d'érythème et le rapport des surfaces d'érythème se sont significativement améliorés par rapport à la référence après 28 et 56 jours d'utilisation d'ETF. CONCLUSION: Cette étude contribue au corpus croissant de littérature soutenant les effets protecteurs des extraits de plantes fermentées contre le stress oxydatif cutané et le vieillissement. En outre, nos résultats pourraient inspirer des efforts pluridisciplinaires pour étudier de nouvelles techniques de fermentation susceptibles de produire des solutions anti­âge encore plus puissantes.

Dynamic Observation of the Coulomb Explosion and Field Evaporation of a Few-Layer Graphene Nanoribbon.

The Coulomb explosion and field evaporation are frequently observed physical phenomena for a metallic tip under an external electric field, which can modify the structures of the tip and have broad applications, such as in the atomic-probe tomography and field ion microscopy. However, the mechanistic comprehending of how they change the structures of the tip and the differences between them are not clear. Here, dynamic observations of Coulomb explosions and field evaporations on the positively biased and charged few-layer graphene (FLG) nanoribbon inside a transmission electron microscope are reported. By combining the atomic-scale molecular dynamic simulations, it is shown that the FLG is split into several sheets under Coulomb explosion. It is also observed to break by emitting the carbon ions/segments under the field evaporation. It is further demonstrated that the split and breaking of FLG can be tuned by the shape of the nanoribbon. FLG ribbons with sharp tips have splitting and breaking occur in sequence. FLG with blunt tips break without a split. These results provide a fundamental understanding of Coulomb explosion and field evaporation in graphene nanomaterials and suggest potential methods to engineer graphene-based nanostructures.

Arrays of horizontal carbon nanotubes of controlled chirality grown using designed catalysts.

The semiconductor industry is increasingly of the view that Moore's law-which predicts the biennial doubling of the number of transistors per microprocessor chip-is nearing its end. Consequently, the pursuit of alternative semiconducting materials for nanoelectronic devices, including single-walled carbon nanotubes (SWNTs), continues. Arrays of horizontal nanotubes are particularly appealing for technological applications because they optimize current output. However, the direct growth of horizontal SWNT arrays with controlled chirality, that would enable the arrays to be adapted for a wider range of applications and ensure the uniformity of the fabricated devices, has not yet been achieved. Here we show that horizontal SWNT arrays with predicted chirality can be grown from the surfaces of solid carbide catalysts by controlling the symmetries of the active catalyst surface. We obtained horizontally aligned metallic SWNT arrays with an average density of more than 20 tubes per micrometre in which 90 per cent of the tubes had chiral indices of (12, 6), and semiconducting SWNT arrays with an average density of more than 10 tubes per micrometre in which 80 per cent of the nanotubes had chiral indices of (8, 4). The nanotubes were grown using uniform size Mo2C and WC solid catalysts. Thermodynamically, the SWNT was selectively nucleated by matching its structural symmetry and diameter with those of the catalyst. We grew nanotubes with chiral indices of (2m, m) (where m is a positive integer), the yield of which could be increased by raising the concentration of carbon to maximize the kinetic growth rate in the chemical vapour deposition process. Compared to previously reported methods, such as cloning, seeding and specific-structure-matching growth, our strategy of controlling the thermodynamics and kinetics offers more degrees of freedom, enabling the chirality of as-grown SWNTs in an array to be tuned, and can also be used to predict the growth conditions required to achieve the desired chiralities.

Atomic-scale observations of electrical and mechanical manipulation of topological polar flux closure.

The ability to controllably manipulate complex topological polar configurations such as polar flux-closures via external stimuli may allow the construction of new electromechanical and nanoelectronic devices. Here, using atomically resolved in situ scanning transmission electron microscopy, we find that the polar flux-closures in PbTiO3/SrTiO3 superlattice films are mobile and can be reversibly switched to ordinary single ferroelectric c or a domains under an applied electric field or stress. Specifically, the electric field initially drives movement of a flux-closure via domain wall motion and then breaks it to form intermediate a/c striped domains, whereas mechanical stress first squeezes the core of a flux-closure toward the interface and then form a/c domains with disappearance of the core. After removal of the external stimulus, the flux-closure structure spontaneously recovers. These observations can be precisely reproduced by phase field simulations, which also reveal the evolutions of the competing energies during phase transitions. Such reversible switching between flux-closures and ordinary ferroelectric states provides a foundation for potential electromechanical and nanoelectronic applications.

Clarifying the Relationship between the Lithium Deposition Coverage and Microstructure in Lithium Metal Batteries.

Improving the reversibility of lithium metal batteries is one of the challenges in current battery research. This requires better fundamental understanding of the evolution of the lithium deposition morphology, which is very complex due to the various parameters involved in different systems. Here, we clarify the fundamental origins of lithium deposition coverage in achieving highly reversible and compact lithium deposits, providing a comprehensive picture in the relationship between the lithium microstructure and solid electrolyte interphase (SEI) for lithium metal batteries. Systematic variation of the salt concentration offers a framework that brings forward the different aspects that play a role in cycling reversibility. Higher nucleation densities are formed in lower concentration electrolytes, which have the advantage of higher lithium deposition coverage; however, it goes along with the formation of an organic-rich instable SEI which is unfavorable for the reversibility during (dis)charging. On the other hand, the growth of large deposits benefiting from the formation of an inorganic-rich stable SEI is observed in higher concentration electrolytes, but the initial small nucleation density prevents full coverage of the current collector, thus compromising the plated lithium metal density. Taking advantages of the paradox, a nanostructured substrate is rationally applied, which increases the nucleation density realizing a higher deposition coverage and thus more compact plating at intermediate concentration (∼1.0 M) electrolytes, leading to extended reversible cycling of batteries.

Dynamics of Polar Skyrmion Bubbles under Electric Fields.

Room-temperature polar skyrmions, which have been recently discovered in oxide superlattice, have received considerable attention for their potential applications in nanoelectronics owing to their nanometer size, emergent chirality, and negative capacitance. For practical applications, their manipulation using external stimuli is a prerequisite. Herein, we study the dynamics of individual polar skyrmions at the nanoscale via in situ scanning transmission electron microscopy. By monitoring the electric-field-driven creation, annihilation, shrinkage, and expansion of topological structures in real space, we demonstrate the reversible transformation among skyrmion bubbles, elongated skyrmions, and monodomains. The underlying mechanism and interactions are discussed in conjunction with phase-field simulations. The electrical manipulation of nanoscale polar skyrmions allows the tuning of their dielectric permittivity at the atomic scale, and the detailed knowledge of their phase transition behaviors provides fundamentals for their applications in nanoelectronics.

Technique and clinical results of a new intramedullary support nail and plate system for fixation of 3- or 4- part proximal humeral fractures in older adults.

BACKGROUND: Internal fixation of complex proximal humeral fractures (PHF) with osteoporosis is associated with a high incidence of complications. This study introduces the technique and clinical results of a novel intramedullary support nail and plate system (ISNPs) for the internal fixation of 3- or 4- part PHF in older adults. The ISNPs combines the concept of intramedullary support and dynamic fixation into a locking plate fixation system that can be applied using a minimally invasive surgical approach. METHODS: A total of 46 consecutive patients diagnosed with 3- or 4-part PHF that met the criteria were included in this study, including 18 in the ISNPs group and 28 in the conventional locking plate (LP) group. Clinical results, including operative time, intraoperative bleeding, reduction quality, subjective outcome ratings, and complications, were compared between the two groups. Functional outcomes were evaluated using the Constant score and disability of the arm, shoulder, and hand (DASH) questionnaire at 1-year follow-up. RESULTS: There were no significant differences in age, sex, local bone quality, Neer-fracture type, and follow-up time between the ISNPs and LP groups. For clinical analysis, there were no significant differences in intraoperative bleeding and operation time between the ISNPs and LP groups. Significant differences were observed in the percentage of the malreduced cases, Constant and DASH score analysis, and the patients' subjective evaluation ('excellent' and 'good' %) between the two groups. CONCLUSION: The ISNPs technique proposed in this study provides a novel hybrid internal fixation model for complex PHF with osteoporosis. The clinical results at 1-year follow-up confirmed the advantage of applying it to 3- or 4- part PHF in older patients. Further studies are required to optimize its design and explore its optimal indications.

Three-Dimensional Limit of Bulk Rashba Effect in Ferroelectric Semiconductor GeTe.

Ferroelectric Rashba semiconductors (FERSCs) have recently attracted intensive attention due to their giant bulk Rashba parameter, αR, which results in a locking between the spin degrees of freedom and the switchable electric polarization. However, the integration of FERSCs into microelectronic devices has provoked questions concerning whether the Rashba effect can persist when the material thickness is reduced to several nanometers. Here we find that αR can keep a large value of 2.12 eV Å in the 5.0 nm thick GeTe film. The behavior of αR with thickness can be expressed by the scaling law and provides a 3D thickness limit of the bulk Rashba effect, dc = 2.1 ± 0.5 nm. Finally, we find that the thickness can modify the Berry curvature as well, which influences the polarization and consequently alters the αR. Our results give insight into understanding the factors influencing αR in FERSCs and pave a novel route for designing Rashba-type quantum materials.

Cation-Deficiency-Dependent CO2 Electroreduction over Copper-Based Ruddlesden-Popper Perovskite Oxides.

We report an effective strategy to enhance CO2 electroreduction (CER) properties of Cu-based Ruddlesden-Popper (RP) perovskite oxides by engineering their A-site cation deficiencies. With La2-x CuO4-δ (L2-x C, x=0, 0.1, 0.2, and 0.3) as proof-of-concept catalysts, we demonstrate that their CER activity and selectivity (to C2+ or CH4 ) show either a volcano-type or an inverted volcano-type dependence on the x values, with the extreme point at x=0.1. Among them, at -1.4 V, the L1.9 C delivers the optimal activity (51.3 mA cm-2 ) and selectivity (41.5 %) for C2+ , comparable to or better than those of most reported Cu-based oxides, while the L1.7 C exhibits the best activity (25.1 mA cm-2 ) and selectivity (22.1 %) for CH4 . Such optimized CER properties could be ascribed to the favorable merits brought by the cation-deficiency-induced oxygen vacancies and/or CuO/RP hybrids, including the facilitated adsorption/activation of key reaction species and thus the manipulated reaction pathways.

Dual Activation of Molecular Oxygen and Surface Lattice Oxygen in Single Atom Cu1 /TiO2 Catalyst for CO Oxidation.

The in-depth mechanism on the simultaneous activation of O2 and surface lattice O2- on one active metallic site has not been elucidated yet. Herein, we report a strategy for the construction of abundant oxygen activation sites by rational design of Cu1 /TiO2 single atom catalysts (SACs). The charge transfer between isolated Cu and TiO2 support generates abundant CuI and 2-coordinated Olat sites in Cu1 -O-Ti hybridization structure, which facilitates the chemisorption and activation of O2 molecules. Simultaneously, the Cu1 -O-Ti induced TiO2 lattice distortion activate the adjacent surface lattice O2- , achieving the dual activation of O2 and surface lattice O2- . The Cu1 -O-Ti active site switches the CO oxidation mechanism from Eley-Rideal (80 °C) to Mars-van Krevelen route (200 °C) with the increase of reaction temperature. The dual activation of O2 and surface lattice O2- can by modulating the electron properties of SACs can boost the heterogeneous catalytic oxidation activity.