Lattice Stability Research Articles

Simultaneous Development of Antiferromagnetism and Local Symmetry Breaking in a Kagome Magnet (Co0.45Fe0.55)Sn.

CoSn and FeSn, two kagome-lattice metals, have recently attracted significant attention as hosts of electronic flat bands and emergent physical properties. However, current understandings of their physical properties are limited to knowledge of the average crystal structure. Here, we report the Fe-doping induced coemergence of the antiferromagentic (AFM) order and local symmetry breaking in (Co0.45Fe0.55)Sn. Rietveld analysis on the neutron and synchrotron X-ray diffraction data indicates A-type antiferromagnetic order with the moment pointing perpendicular to the kagome layers, associated with the anomaly in the MSn(1)2Sn(2)4 (M = Co/Fe) octahedral distortion and the lattice constant c. Reverse Monte Carlo (RMC) modeling of the synchrotron X-ray total scattering results captured the subtle local orthorhombic distortion involving off-axis displacements of Sn(2). Our results indicate that the stable hexagonal lattice above TN becomes unstable once the A-type AFM order is formed below TN. We argue that the local symmetry breaking has a magnetic origin, since the spatially varied M-Sn(2) bond lengths arise from out-of-plane magnetic exchange coupling Jc via the exchange pathway M-Sn(2)-M. Our study provides comprehensive information on the crystal structure in both long-range scale and local scale, unveiling unique coupling between AFM order, octahedral distortion, and hidden local symmetry breaking.

First-principles study on a new 2D carbon allotrope with an intrinsic wide bandgap: A comparison with α-graphyne

Nanocarbon materials with intrinsic electronic bandgaps are highly desirable for next-generation carbon-based nanoelectronics. Herein, a new two-dimensional (2D) carbon allotrope with structural similarities to α-graphyne has been proposed theoretically, which exhibits intrinsic semiconducting behavior with a wide direct bandgap significantly larger than that reported in other 2D carbon allotropes. Based on first-principles calculations, the structural and electronic properties of the new 2D carbon allotrope, as well as its lattice stability, have been systematically investigated by adopting a comparative study with α-graphyne. Moreover, the effects of vertical stacking and in-plane biaxial strain on the new 2D carbon allotrope have also been clarified in this work, providing robust approaches for the effective modulation of electronic properties in the new 2D carbon allotrope. Thus, the intrinsic wide bandgap, along with effective modulations, suggests great advantages and potentials of the new 2D carbon allotrope in carbon-based electronic devices and light-emitting applications.

Probing Abrikosov vortices in niobium with single nitrogen-vacancy centers in nanodiamonds

Abrikosov vortices play a fundamental role in the magnetic and electric properties of superconductors. The study of their pinning forces is essential to better understand the stability of vortex lattices, with the aim of increasing critical currents in superconductors. However, the study of vortices is challenging because of their nanometric sizes and the large variation in the pinning forces. In this Letter, we use a single nitrogen-vacancy center in a nanodiamond as a nanoscale magneto sensor to locally probe single vortices and their pinning effects in a thin niobium film. This simple, far-field optical approach also offers the possibility of manipulating a single spin with a single flux quantum.

Progress, application and prospect of rare earth-based perovskite light-emitting diodes

Perovskites recently become star materials in light-emitting diodes (LEDs) field due to their high color purity, tunable emission spectra, and cost-effectiveness. However, the commercial applications of perovskite LEDs are hampered by inferior lattice stability of perovskite materials. Successful modification of functional materials is a promising strategy towards efficient and stable perovskite LEDs. Rare earth (RE) metals are incorporated into the perovskite lattice, including double perovskites, by occupying the B-site or A-site in perovskite such as ABX3 or A2BB'X6, forming the RE-based perovskite. Doping with RE ions enables precise control emission color of materials across a broad spectrum ranging from ultraviolet to near infrared. Moreover, this strategy reduces the energy loss in electron relaxation process and enhances electroluminescence intensity of LED device, thereby improving the potential of commercial applications of perovskite LEDs. This review provides a comprehensive and systematic summarization of recent progress and challenges in RE-based perovskite materials (structure types, luminescence mechanism and synthesis methods) and LEDs (device structures and main applications) to provide some enlightening insights for realization of efficient and stable RE-based perovskite LEDs.

The influence of parasitic modes on stable lattice Boltzmann schemes and weakly unstable multi-step Finite Difference schemes

Numerical analysis for linear constant-coefficient multi-step Finite Difference schemes is a longstanding topic, developed approximately fifty years ago. It relies on the stability of the scheme, and thus—within the L2 setting—on the absence of multiple roots of the amplification polynomial on the unit circle. This allows for the decoupling, while discussing the convergence of the method, of the study of the consistency of the scheme from the precise knowledge of its parasitic/spurious modes, so that the methods can be essentially studied as if they had only one step. Furthermore, stability alleviates the need to delve into the complexities of floating-point arithmetic on computers, which can be challenging topics to address. In this paper, we demonstrate that in the case of “weakly” unstable Finite Difference schemes with multiple roots on the unit circle, although the schemes may remain stable, considering parasitic modes is essential in studying their consistency and, consequently, their convergence. This research was prompted by unexpected numerical results on stable lattice Boltzmann schemes, which can be rewritten in terms of multi-step Finite Difference schemes. Unlike Finite Difference schemes, rigorous numerical analysis for lattice Boltzmann schemes is a contemporary topic with much left for future discoveries. Initial expectations suggested that third-order initialization schemes would suffice to maintain the accuracy of fourth-order schemes. However, this assumption proved incorrect for weakly unstable Finite Difference schemes and for stable lattice Boltzmann methods. This borderline scenario underscores that particular care must be adopted for lattice Boltzmann schemes, and the significance of genuine stability in facilitating the construction of Lax-Richtmyer-like theorems and in mastering the impact of round-off errors concerning Finite Difference schemes. Despite the simplicity and apparent lack of practical usage of the linear transport equation at constant velocity considered throughout the paper, we demonstrate that high-order lattice Boltzmann schemes for this equation can be used to tackle nonlinear systems of conservation laws relying on a Jin-Xin approximation and high-order splitting formulæ.

A Multisite Atomic‐Oxygen Anchoring Strategy Affords Efficient and Stable Perovskite Solar Cells

AbstractLewis base molecules are widely used to passivate structural defects in perovskites. However, the spatial compatibility between these molecules and the perovskite lattice is seldom considered. Herein, a multisite atomic‐oxygen (O) anchoring passivation strategy using 1,1,2,2‐tetra(4‐methoxyphenyl)ethene (TMPE), which contains four electronegative O atoms to selectively anchor iodine vacancies and passivate under‐coordinated Pb2+ or MA+ defects is proposed. It is found that the distance between any three O atoms in a TMPE molecule matches that of iodine ions in the lattice structure, thereby maximizing passivation effects and enhancing lattice stability. Additionally, the coordination of TMPE facilitates the formation of larger colloid sizes in the precursor solution, effectively regulating crystal growth. Due to the molecular extrusion effect, TMPE‐based anchors localize on the surface, passivating defects and mitigating nonradiative recombination. As a result, defects in MA‐based and FA‐based perovskite films are significantly reduced, achieving optimized power conversion efficiencies (PCEs) of 19.9% and 24.5%, while exhibiting exceptional stability by retaining 90% of initial PCE after 1200 h of storage without encapsulation. This single molecule‐controlled perovskite multisite anchoring strategy would help resolve lattice stability issue caused by perovskite defects, thereby paving the pathway for the development of high‐performance and highly stable perovskite solar cells.

Reversible Configurations of 3-Coordinate and 4-Coordinate Boron Stabilize Ultrahigh-Ni Cathodes with Superior Cycling Stability for Practical Li-Ion Batteries.

Ultrahigh-Ni layered oxide cathodes are the leading candidate for next-generation high-energy Li-ion batteries owing to their cost-effectiveness and ultrahigh capacity. However, the increased Ni content causes larger volume variations and worse lattice oxygen stability during cycling, resulting in capacity attenuation and kinetics hysteresis. Herein, a Li2SiO3-coated Li(Ni0.95Co0.04Mn0.01)0.99B0.01O2 ultrahigh-Ni cathode that well-addresses all the above issues, which is also the first time to realize the real doping of B ions is demonstrated. The as-obtained cathode delivers a reversible capacity of up to 237.4 mAh g-1 (924 Wh kg-1 cathode) and a superior capacity retention of 84.2% after 500 cycles at 1C in pouch-type full-cells. Advanced characterizations and calculations verify that the boron-doping is existed in terms of 3-coordinate and 4-coordinate configurations and their high electrochemical reversibility during de-/lithiation, which greatly stabilizes oxygen anions and impedes Ni-ion migration to Li layer. Furthermore, the B-doping engineers the primary particle microstructure for better relaxing the lattice strain and accelerating Li-ion diffusion. This work advances the energy density of cathode materials into the domain of above 900 Wh kg-1, and the concept will inspire more intensive study on ultrahigh-Ni cathodes.

Enhancing electrochemical performance of high-entropy Co/Ni-free P2/O3 hybrid-phase layered metal oxide cathode for sodium-ion batteries

Sodium-ion batteries (SIBs) have currently garnered increasing attention due to their promising applications and potential advantages. Despite the cost and performance advantages, the Co/Ni-free Fe-Mn-based cathode materials tends to undergo a large phase transition in the sodium (de)intercalation layer, which will result in the material structure damage. In this work, high entropy P2/O3-Na0.75Cu0.1Fe0.2Mg0.2Mn0.4Ti0.1O2 (NCFMMT) materials were successfully prepared by employing NaTi2(PO4)3 (NTP) as the modification layer. It can be distinctly seen that the cyclic stability of NCFMMT@NTP has been significantly improved, and the first capacity at 0.2C reaches 165.32 mAh/g and the capacity can maintain 86.73 % after 100 cycles. Moreover, the voltage hysteresis after triggering anionic redox can be clearly ameliorated. Apparently, the high-entropy strategy not only can satisfactorily optimize the lattice structure and stability of the cathode material during sodium intercalation/de-intercalation process, but also can increase the ion mobilization rate and promote further electrochemical properties. Therefore, this study provides valuable exploration for the design and preparation of cobalt/nickel-free cathodes with excellent electrochemical performance.

Pressure-induced band gap enhancement and temperature-dependent thermoelectric characterization of semiconducting Transition Metal Chalcogenides LiMS (M = Cu, Ag)

The first principles study of Transition Metal Chalcogenides LiMS (M = Cu, Ag) has been conducted utilizing the concepts of Density Functional Theory (DFT). Both the compounds possess a cubic structure with space group F-43m. The mechanical stability of LiCuS and LiAgS has been predicted based on the values of elastic tensor. These Chalcogenides possess an interesting electronic band structure which reveals their semiconducting nature with a direct band gap. The electronic structure is further subjected to high pressure and the changes in band gap are deeply observed. For these materials, the changes in band gap in response to applied pressure suggest the possibility of their use in band gap engineering. The phonon curves are investigated over the Brillouin zone's high symmetry directions which reveal the lattice dynamical stability of the presently studied compounds. Moreover, the atoms present at different positions inside a crystal lattice exhibit vibrations of different intensities and in different directions which have been studied through the Eigenvector representations. The thermoelectric properties of LiCuS and LiAgS have been characterized using Boltzmann's theory over the range of temperature between 100 K and 1600 K. The calculated thermoelectric parameters reveal the high thermoelectric efficiency of these materials with excellent values of the figure of merit. The interesting properties of ternary Chalcogenides LiMS (M = Cu, Ag) make them promising candidates for thermoelectric applications.

Phase Heterojunction by Constructing Built‐In Electric Field toward Sodium‐Rich Cathode Material

AbstractAn artificial built‐in electric field from phase heterojunction is constructed within sodium‐rich manganese‐based layer‐structured oxide O3‐Na[Ni0.3Mn0.55Cu0.1Ti0.05]O2@Na2MoO4 through shared oxygen atoms. The spinel Na2MoO4 phase behaves as a p‐type semiconductor, while the O3‐Na[Ni0.3Mn0.55Cu0.1Ti0.05]O2 phase functions as an n‐type semiconductor. It can efficiently reduce the diffusion barrier and enhance electron transport, which can adequately promote the interfacial desolvation ability and reduce bulk lattice strains. The formed spinel heterostructure with crystal structure stability can also enhance the interface Na+ diffusion and protect the electrode against moisture and carbon dioxide corrosion. Besides, the molybdenum introduction within the lattice bulk can enhance the bond covalency, fortifying lattice oxygen stability and restraining structural distortion effectively. The obtained cathode demonstrates a high up to 224.61 mAh g−1 discharge specific capacity at 0.1 C and a long cycle stability with a 60.44% capacity retention after 265 cycles at 0.5 C. This study illuminates the potential of Na‐rich Mn‐based oxide cathodes for high‐energy‐density sodium battery utilizations.

Crystal Structure, Supramolecular Organization, Hirshfeld Analysis, Interaction Energy, and Spectroscopy of Two Tris(4-aminophenyl)amine-Based Derivatives

The use of tris(4-aminophenyl)amine (TAPA) as central to the synthesis of both polyimines and polyimides and covalent organic frameworks and inorganic cages, among others, has grown in the last few years. The resulting materials exhibit high performance in their area of application. In this contribution, the crystal structures of two TAPA derivatives, triethyl (nitrilotris(benzene-4,1-diyl))tricarbamate (1) and triethyl 2,2′,2″-((nitrilotris(benzene-4,1-diyl))tris(azanediyl))tris(2-oxoacetate) (2), are described. The molecular and supramolecular structures of both compounds were compared between them and with analogous compounds. The analyses of their vibrational and 13C-CPMAS NMR spectroscopies, as well as their thermal stability, were included and corelated with the crystal structure. Hirshfeld surface analysis on the crystal structures of both TAPA derivatives revealed the stabilization of the crystal network via the amide N—H∙∙∙O interactions of dispersive nature in the carbamate, whereas dispersive carbonyl–carbonyl interactions also played a competitive role in the supramolecular arrangement of the oxamate. Interaction energy DFT calculations performed at the B3LYP/6-31G(d,p) level allowed us to estimate the energy contributions and nature of several interactions in terms of the stability of both crystal lattices.

Highly Stable Lattice Boltzmann Method with a 2-D Actuator Line Model for Vertical Axis Wind Turbines

Highly Stable Lattice Boltzmann Method with a 2-D Actuator Line Model for Vertical Axis Wind Turbines

Synthesis, crystal structure, spectral analysis and NLO studies of five-coordinate Zn(II) complexes of hydrazochromandione

Using a hydrazochromandione ligand, a straightforward chemical process is used to create zinc(II) complexes (1 and 2) with five coordination. Elemental microanalysis and a range of spectroscopic techniques (FT-IR, 1H NMR and electronic spectroscopy) were used to characterize the ligand and Zn(II) complexes. Single crystal X-ray diffraction was used to identify the crystal structures of HL, complex 1 and 2, and the results showed that ligand has monoclinic system with centrosymmetric space group P21/n. Through ONO donor atoms, Zn(II) metal is coordinated to the ligand in the same way as monoanionic. Two Zn(II) complexes with a deformed square pyramidal geometry surrounding them. Interestingly, relatively strong hydrogen bonds and p-p interactions that result in supramolecular architectures preserve the stabilization of the crystal lattices. Comparing two Zn(II) complexes to hydrazochromandione ligand, they exhibit good non-linear optical response.

Effect of sites of doped Mg on the stability of lattice oxygen in lithium-rich manganese-based cathode materials

Elemental doping is considered as an effective method for altering the localized electronic structure of lattice oxygen in lithium-rich manganese-based oxides (LRMO) and enhancing their structural stability. However, the effect of doping heteroatoms at different sites on the oxygen redox is not clear. In this work, Mg is introduced into transition metals (TM) and lithium (Li) sites of LRMO at co-precipitation stage and lithiation stage to prepare LRMO-TM and LRMO-Li, respectively. The experimental results and density-functional theory calculations demonstrate that the oxygen release is reduced from 4.1653 nmol mg−1 of pristine to 3.3886 nmol mg−1 of LRMO-Li, and 2.7688 nmol mg−1 of LRMO-TM. The reduction of oxygen release of LRMO-Li is related to the formation of strong Mg-O interactions. Different from that, the lower oxygen release of LRMO-TM is mainly due to the reduction of electron holes in the O 2p state caused by the weaker Mn-O covalency, which effectively restricts the over-oxidization of oxygen. The capacity retention of LRMO-TM is 85.18 % at 0.2C after 200 cycles, which is higher than that of LRMO (78.63 %) and LRMO-Li (82.28 %). This work reveals the mechanism of enhancing lattice oxygen stability caused by Mg doping at different sites.

Discovering novel γ-γ′ Pt-Al superalloys via lattice stability in Pt3Al induced by local atomic environment distortion

The strength of Pt-Al superalloys can be effectively improved using a coherent structure composed of a disordered γ phase and an ordered γ′ phase. However, γ′-Pt3Al has a cubic phase only at high temperatures and a tetragonal phase at low temperatures, thus breaking the coherent interface and deteriorating its mechanical properties. Here, high throughput first-principles calculations and rational experiments were conducted to discover novel γ-γ′ Pt-Al superalloys. The alloying strategy stabilizes the γ′ phase through the local charge distortion (LCD) or the local lattice distortion (LLD). Alloying elements, such as, Ti, Hf, and Ta, occupy the Al site in combination with Pt, making the spherical shape of change density in Pt3Al showing obvious directionality, i.e., LCD. Therefore, the stability of the γ′ phase is proposed at a lower alloying element concentration (3.125 at.%). However, alloying elements near Pt, e.g., Ni, Co, and Ru, tend to occupy the Pt site and induce LLD to stabilize the γ′ phase at higher alloying element concentration (12.5 at.%). The shape of the change density is similar to that of Pt3Al, and no obvious LCD is found when alloying elements occupy the Pt site. LCD-induced phase stability is observed exclusively at the Al site, whereas LLD-induced phase stability is solely present at the Pt site. The Pt-12Al-6X (X = Hf, Ti, Ta, Cr, and Ni in at.%) alloys were prepared, among which Pt-12Al-6Hf possessed a stable γ′ phase, a lower lattice misfit between γ and γ′, and a higher precipitation strengthening, resulting in its hardness (442.1 HV) surpassing that of Ni-based superalloys IN718 (413.6 HV). The γ′ phase in Pt-12Al-6Hf was characterized by high-resolution transmission electron microscopy, suggesting that the Pt site of the γ′ phase was occupied by Pt, while the Al site was shared by Pt, Al, and Hf. This is consistent with the calculated results.

Evolution of the Fermi Surface of 1T-VSe2 across a Structural Phase Transition.

Periodic lattice distortion, known as the charge density wave, is generally attributed to electron-phonon coupling. This correlation is expected to induce a pseudogap at the Fermi level in order to gain the required energy for stable lattice distortion. The transition metal dichalcogenide 1T-VSe2 also undergoes such a transition at 110 K. Here, we present detailed angle-resolved photoemission spectroscopy experiments to investigate the electronic structure in 1T-VSe2 across the structural transition. Previously reported warping of the electronic structure and the energy shift of a secondary peak near the Fermi level as the origin of the charge density wave phase are shown to be temperature independent and hence cannot be attributed to the structural transition. Our work reveals new states that were not resolved in previous studies. Earlier results can be explained by the different dispersion natures of these states and temperature-induced broadening. Only the overall size of the Fermi surface is found to change across the structural transition. These observations, quite different from the charge density wave scenario commonly considered for 1T-VSe2 and other transition metal dichalcogenides, bring fresh perspectives toward correctly describing structural transitions. Therefore, these new results can be applied to material families in which the origin of the structural transition has not been resolved.

Insights into effects of Fe doping on phase stability, martensitic transformation, and magnetic properties in Ni-Mn-Ti-Fe all-d-metal Heusler alloys

In this work, the effects of Fe doping on phase stability, martensitic transformation, and magnetic properties of Ni50Mn37.5-xTi12.5Fex (x = 3.125, 6.25, 9.375) all-d-metal Heusler alloys were systematically investigated by first-principles calculations. The results indicate a tendency for doped Fe atoms to aggregate within the Ni50Mn37.5-xTi12.5Fex alloys. As Fe concentration increases, a gradual reduction in both lattice constants and phase stability of austenite and martensite is observed. In the absence or presence of minimal Fe doping, both austenite and martensite exhibit antiferromagnetic behavior. However, at x = 9.375, a transition to a ferromagnetic state is observed in the austenite phase. This transition is attributed to the activation of the ferromagnetic coupling effect in the austenite phase induced by Fe doping in the Ni-Mn-Ti alloy. In contrast, the martensite phase maintains its antiferromagnetic characteristics throughout the doping range. A comprehensive analysis of the electronic structure elucidates the underlying physical mechanisms responsible for the martensitic transformation and magnetic property changes.

Use of third generation data for the pure elements to model the thermodynamics of binary alloy systems: Part 3 – The theoretical prediction of the Al–Si–Zn system

In a previous paper a method was developed to define Einstein temperatures for metastable phases of the elements and their relation to the so-called lattice stabilities used in the past, and also the variation of the Einstein temperature with composition to account for the composition dependence of the excess entropy. This approach was demonstrated successfully for the Al–Zn system. In this paper this approach is extended to cover the Al–Si and Si–Zn binary systems. The phase diagram for the Al–Si–Zn ternary system was then predicted from the thermodynamic description of the binary subsystems only without any ternary interaction parameters. Agreement with the experimental data is shown to be very good.

Loop current states and their stability in small fractal lattices of Bose-Einstein condensates

Loop current states and their stability in small fractal lattices of Bose-Einstein condensates

High-performance single crystal Ni-rich cathode with regulated lattice and interface constructed by separated lithiation and crystallization calcination

Incorporating high valence dopants, such as W6+ and Mo6+ has been verified to be effective for tuning the microstructure and grain boundary of polycrystal Ni-rich cathode. However, the hindered consolidation of primary particles induced by dopants during lithiation calcination limits the utilization of those dopants to crystalize single-crystal Ni-rich cathodes with stabilized lattice and surface. Herein, high performance single crystal LiNi0.84Co0.11Mn0.05O2 cathode with Al3+ and W6+ regulated lattice and boundary phase was construed based on commercial process with two-step calcination process containing separated lithiation and crystallization. The introduction of appropriate amount of Al3+ in the first lithiation calcination of 6 h endows the bulk of crystalline with enhanced lattice stability, while the incorporation of W6+ with stoichiometrical LiOH in the secondary crystallization calcination of 6 h renders uniformly distributed surface layer without hampering the growth of single-crystal. With the Al3+ doped bulk lattice, W6+ doped subsurface region and hetero-epitaxially grown Li2WO4, the cathode infused by two-step calcination exhibits high discharge capacity, rate performance, and cycling stability. Specifically, the modified LiNi0.84Co0.11Mn0.05O2 exhibits exceptional capacity retention, maintaining 88.98% of its initial capacity after 200 cycles at a rate of 1 C within a voltage window of 2.7–4.3 V at a temperature of 25 °C in half-cell. This performance is markedly superior to the capacity retention of 72.96% observed for pristine cathode. Even when subjected to a stringent test after 200 cycles at the same rate, the modified cathode sustains an impressive capacity retention of 82.41% at an elevated cut-off voltage of 4.5 V and a temperature of 30 °C.