Search Results (791)

Vanadium borate (V₃BO₆) has recently been synthesized and identified as a promising material for use in energy storage applications, particularly as a potential anode for lithium-ion batteries. However, despite previous studies highlighting its electrochemical performance, a comprehensive understanding of its intrinsic mechanical, thermal, and vibrational properties remains limited. The compound crystallizes in an orthorhombic phase with the Pnma (No. 62) space group. To explore its intrinsic physical characteristics, full geometry optimization of the unit cell and atomic positions was performed using density functional theory (DFT) within the CASTEP framework. The Perdew–Burke–Ernzerhof (PBE) functional under the generalized gradient approximation (GGA) was used to model exchange–correlation effects. A plane-wave cut-off of 408 eV and a 6 × 6 × 13 Monkhorst–Pack grid were employed to ensure numerical convergence. The optimized lattice constants (a = 9.9025 Å, b = 8.4751 Å and c = 4.5354 Å) are highly consistent with experimental data, which confirms the reliability of the computational approach adopted. The elastic behaviour was further investigated using the first-principles strain-energy method, yielding nine independent elastic constants consistent with orthorhombic symmetry. The calculated bulk and shear moduli, along with the anisotropy parameters, suggest that V₃BO₆ has a favourable balance of mechanical robustness and moderate ductility. A Vickers hardness of 10.95 GPa and a B/G ratio of approximately 1.93 corroborate these findings. Additional parameters, such as Poisson’s ratio, Debye temperature and average sound velocities, were derived to gain deeper insight into the material’s thermomechanical performance. These results provide a solid theoretical foundation for understanding the mechanical stability and potential anode suitability of V₃BO₆ in lithium-ion battery systems. Full article

The pure and xDy³⁺-doped SrMoO₄ series (x = 0.5, 1.0, 1.5 and 2.0 at.%) were synthesized using a direct mechanochemical route. We found that a milling speed of 850 rpm and a milling time of 30 min result in a complete chemical reaction at different concentrations of dopant ions. The phase formation, structural units, and optical properties of the obtained samples were investigated by XRD, IR, UV-Vis and PL analyses. It has been established that Dy₂O₃ mainly influences the lattice parameters, unit cell volumes, crystallite sizes, and microstrains. The symmetry of MoO₄ groups was investigated using IR spectroscopy, and it showed that pure and Dy³⁺-doped SrMoO₄ samples are built up of deformed structural units. The calculated optical band gap of the obtained crystal phases decreases with increasing concentrations of Dy³⁺ ions. The host SrMoO₄ matrix shows broad blue emission centered at 430 nm under an excitation wavelength of 230 nm. All doped samples display a strong yellow emission at 570 nm, belonging to the ⁴F_9/2 → ⁶H_13/2 transition of Dy³⁺ ions. The highest luminescence intensity was observed when the concentration of the Dy³⁺ ion was 0.5 at.%. The mechanism of concentration quenching was mainly caused by the electric dipole–dipole interaction. The calculated CIE chromaticity coordinates of the doped samples fall in the yellow range. This study demonstrates that mechanochemical treatment is an appropriate route for the fast preparation of yellow phosphors. Full article

[Mn^III(pyrol)₃(tren)] {(Hpyrol)₃tren = tris(1-(2-azolyl)-2-azabuten-4-yl)amine)} is a mononuclear spin-transition compound switching between high spin (HS, S = 2) and low spin (LS, effective S = 1) around 47 K, preserving I$\overline{4}$3d symmetry. Its magnetic anisotropy is studied by calculating the atomic susceptibility tensor from the refinement of polarized neutron powder diffraction. The analysis reveals that the weakly prolate-type atomic magnetic anisotropy in the HS state abruptly switches to uniaxial needle-shaped/Ising-type anisotropy in the LS state. However, the overall magnetic anisotropy of the unit cell remains isotropic due to the cubic nature of the crystal symmetry. Irreversible coexistence of mixed spin states HS/LS is observed in the vicinity of the cooperative spin crossover, where the average magnetic moment of Mn³⁺ shows a hysteretic temperature variation. This hysteretic mixing of HS and LS at intermediate temperatures suggests complex growth and nucleation of HS and LS domains. The study demonstrates that polarized powder neutron diffraction is a unique and powerful tool for describing complex magnetic anisotropies and magneto-structural correlations in molecular-based magnetic materials. Full article

Co²⁺-doped CsPbI₃ nanocrystals (NCs) (CsPbI₃:xCo, x = 0, 5, and 10 mol%) were synthesized in situ within a borosilicate glass matrix by the fusion method followed by controlled thermal treatment at 500 °C for 6–24 h. Transmission electron microscopy images showed quasi-spherical NCs with mean diameters of 4.9–7.1 nm. Energy-dispersive X-ray spectroscopy suggested cobalt incorporation within the nanocrystalline regions. X-ray diffraction patterns confirmed the exclusive stabilization of the cubic α-phase across all compositions, with systematic lattice contraction from a = 6.321 Å to a = 6.301 Å with increasing Co content, consistent with preferential B-site substitution of Pb²⁺ by Co²⁺. Transmittance measurements confirmed macroscopic optical transparency of all glass-NC composites after thermal treatment. The crystal field theory and Tanabe–Sugano analysis for d⁷ ions in tetrahedral (Td) symmetry yielded Δ = 5032 cm⁻¹ and B = 725 cm⁻¹ in the as-prepared state, evolving to Δ = 4428 cm⁻¹ and B = 805 cm⁻¹ after thermal treatment, confirming Td Co²⁺ coordination and significant metal–iodide covalency. CIE 1931 chromaticity analysis revealed tunable emission from deep-red coordinates to near-white-light regions, demonstrating potential for LED and single-material WLED phosphor applications. Long-term photoluminescence measurements demonstrated full preservation of α-phase excitonic emission after approximately 365 days under ambient conditions, establishing the robust phase stability of CsPbI₃:xCo NCs embedded in borosilicate glass. Full article

The formation and growth of isolated domains during local switching by a biased tip of a scanning probe microscope in a (100) cut of a bismuth titanate Bi₄Ti₃O₁₂ single crystal were studied experimentally. The as-grown domain structure consists of two domain types: a-type (out-of-plane) and b-type (in-plane). Local switching of the a-type domain area leads to anisotropic growth of a hexagonal a-type domain (a-a switching) with 180° walls. The dependence of the domain size on the pulse duration during domain growth along the b-axis was considered in terms of the anisotropic current-limited domain wall motion. Local switching of the b-type domain area leads to formation of a hexagonal a-type domain (b-a switching) with 90° walls increasing in size linearly with the applied voltage. The dependence of the domain size on the pulse duration was measured over a wide range of humidities. The increase in the domain size at moderate humidity is attributed to the effect of the water meniscus. The decrease in the domain size at high humidity is attributed to backswitching under the action of the residual depolarization field, facilitated by a conductive water layer on the side surfaces of the sample. The obtained results provide useful insights into the domain kinetics of ferroelectrics with C₂ symmetry and can pave the way for the development of domain engineering techniques. The obtained results establish a direct relationship between local switching kinetics, crystallographic anisotropy, and environmental conditions. This provides the scientific community with a new framework for understanding domain wall motion in multiaxial ferroelectrics, which is essential for the development of stable and reliable domain-engineered devices. Full article

The article investigates the dielectric and conductive properties of the polar α-phase of Na₃Fe₂(PO₄)₃ polycrystals synthesized by solid-phase (sample type 1), melt (type 2), and melt-quenching (type 3) methods. To enable a rapid assessment of the dielectric properties of the polar α-phase of Na₃Fe₂(PO₄)₃, the thermo-polarization mobility parameter μ_Tp(T, E(ω)) was introduced. By studying the dielectric properties, it was concluded that the polar α-phase of type 1 samples consists of large and small dipoles and ordered sodium cations, which possess low values of μ_Tp(T, E(ω)), indicating the presence of strong interaction forces between the crystal lattice and the cationic part of the polycrystal. Additional studies of the samples’ conductivity confirm this conclusion. Studies of the polar α-phase of Na₃Fe₂(PO₄)₃ in type 2 samples have established that their structure contains dipoles and sodium cations with higher values of μ_Tr(T, E(ω)), and also exhibits higher conductivity than Type 1 samples. These data indicate a weakening of the interaction forces between the cationic and anionic components in type 2 polycrystals due to a partial increase in crystal symmetry. The results of studies of the polar α-phase of type 3 samples show that their structure contains dipoles and sodium cations with higher values of μ_Tr(T, E(ω)), and also exhibits higher conductivity than type 2 samples. It is concluded that the structure of type 3 samples is characterized by weak interaction forces between the cationic and anionic parts as a result of an increase in the symmetry of the polar α-phase of Na₃Fe₂(PO₄)₃, caused by sharply graded temperature conditions during the synthesis of polycrystals. By studying the dielectric properties of cathode materials, it is possible to obtain information on the extent of interactions between the cationic and anionic components in polycrystals. It is, therefore, appropriate to use this approach when investigating a wide range of new dielectric and ion-conducting materials. Full article

Traditional analyses of transport phenomena rely on prescribed geometric boundaries, yet natural flow systems dynamically evolve their architecture to maximize access to currents. To address this disparity, we propose a field-theoretic framework for the constructal law that treats physical geometry as a dynamic state variable, represented by a time-dependent conductivity tensor. Using a variational approach grounded in non-equilibrium thermodynamics, we derive a general tensor evolution equation. Within this framework, macroscopic flow architecture emerges deterministically from the continuous competition between non-linear flux-induced accretion, linear entropic relaxation, and spatial smoothing. Scaling analysis reduces this dynamic to a tri-parameter dimensionless phase space: a morphogenic number driving structural growth, a structural diffusion number governing spatial coherence, and a stochastic intensity number providing the microscopic seeds for symmetry breaking. Our principal result is the analytical prediction of a critical bifurcation. When the local morphogenic number strictly exceeds unity, the system escapes its stable, isotropic configuration and branches into highly conductive, anisotropic architectures. We demonstrate the predictive validity and trans-scalar applicability of this continuum theory by mapping it to highly diverse phase transitions, successfully capturing phenomena ranging from microscopic aerosol agglomeration and microbial resistance, to macroscopic coral plasticity and crystal growth instabilities, and finally to the astrophysical launching of relativistic jets from black holes. Full article

While macroscopic stress significantly impacts the performance of metallic components, the underlying atom–electron coupling mechanisms governed by distinct crystal symmetries remain insufficiently understood. To address this gap, this work systematically investigates the structural and electronic evolution of representative metallic materials under applied stress. Experimentally, X-ray diffraction (XRD) revealed complex macroscopic residual stress distributions in cold rolled titanium alloy and silicon steel. Motivated by these engineering observations, first-principles density functional theory (DFT) calculations were conducted to uncover the underlying physical mechanisms. Specifically, the responses of face-centered cubic (FCC) aluminum and copper, body-centered cubic (BCC) iron, and hexagonal close-packed (HCP) titanium crystals were investigated under tension and compression using the RPBE functional. Stress-dependent elastic properties, density of states (DOS), band structures, and phonon spectra were calculated. Results show that tension softens all metals (Al becomes mechanically unstable), whereas compression stiffens their lattices. Electronically, tensile loading sharpens DOS peaks near the Fermi level and shifts conduction bands closer to it, whereas compression smooths DOS peaks and shifts bands away. Phonon analysis indicates Cu and Ti remain dynamically stable, while Al and Fe exhibit phonon mode softening under high tension. These stress-induced changes highlight crucial atom–electron coupling mechanisms, providing a theoretical basis for tailoring metallic performance via stress engineering. Full article

Polyhalite, K₂SO₄•MgSO₄•2CaSO₄•2H₂O, a ternary evaporite mineral, is commonly found in evaporitic rock salt strata, where it acts as an indicator mineral for potash evaporite deposits. As a directly exploitable mineral potash fertilizer, polyhalite serves as an important substitute for potassium resources. The thermodynamic properties of polyhalite remain poorly characterized experimentally; consequently, current estimates predominantly rely on predictive modeling and indirect experimental approaches. The Raman spectra of free SO₄²⁻ vibrational modes in various sulfate minerals are sensitive to the local symmetry and hydrogen-bonding environment within crystal hydrates, and are directly influenced by the surrounding crystal field. This sensitivity makes Raman spectroscopy a powerful tool for investigating and identifying the crystal structures of sulfate minerals. In this work, the thermodynamic and Raman vibrational properties of polyhalite were investigated using density functional theory (DFT). Phonon calculations at the optimized geometry were employed to compute polyhalite’s key thermodynamic properties—specific heat, entropy, enthalpy, Gibbs free energy, and Debye temperature—over a temperature range of 0–1000 K. The results showed that: (1) the computed volume exhibited minimal error, approximately 0.87%, compared to experimental data; (2) the calculated values for the isobaric heat capacity and entropy were 420.72 and 531.39 J·mol⁻¹·K⁻¹ at 298.15 K, respectively; and (3) the calculated value for the free energy of formation at 298.15 K was −5670 kJ·mol⁻¹. The computed Raman spectrum results showed that the typical spectral features of polyhalite are: (1) ν1 for 1024 cm⁻¹, symmetric stretching mode; (2) ν2 for 464 cm⁻¹, symmetry bending mode; and (3) ν4 for 627 cm⁻¹, anti-symmetry bending mode. Full article

It is found that the speckle structure of the photoinduced light scattering indicatrix of the LiNbO₃:Y³⁺(0.46 wt%) crystal and its behavior with the time of crystal irradiation with a laser undergo an atypical behavior caused by the features of the dissipation processes of laser-induced defects in the crystal. In the frequency range of 100–4000 cm⁻¹, the Raman spectra of the LiNbO₃:Y³⁺(0.46 wt%) single crystal were recorded upon excitation by visible (532 nm) and near-IR (785 nm) laser radiation. Five second-order Raman scattering lines were detected in the frequency range of 1000–2100 cm⁻¹, with the frequencies of two of them (of about 1790 cm⁻¹ and 1940 cm⁻¹) somewhat exceeding the doubled value of the frequencies of fundamental vibrations of the 4A₁(z)LO (longitudinal optical) and 9E(x,y) symmetry types, which allows us to attribute these lines to the overtones of the fundamental vibrations of 4A₁(z)LO and 9E(x,y). It is found that only one Raman scattering line is observed in the region of stretching vibrations of OH-groups (3200–3800 cm⁻¹). The frequency of this line is found to depend on the scattering geometry, varied within 3431–3438 cm⁻¹, and to be shifted to the low-frequency region by about 30–50 cm⁻¹ relative to the frequencies in the IR absorption spectrum. This finding may be due to the alternative prohibition rule due to the presence of the center of symmetry of the oxygen octahedra O₆ of the crystal structure. Full article

The study presents a comprehensive first-principles investigation of the structural, electronic, and magnetic properties of rocksalt scandium nitride (ScN) and its Cr- and Mn-doped derivatives using spin-polarized density-functional theory within the GGA + U (U_Cr = 3.5 eV, U_Mn = 2.7 eV) and HSE06 frameworks. Pristine ScN crystallizes in the cubic Fm$\bar{3}$m structure and exhibits narrow-gap semiconducting behavior, with an indirect band gap of 0.82 eV obtained from hybrid-functional calculations, in excellent agreement with reported theoretical values. Substitutional doping with Cr and Mn introduces localized 3d states near the Fermi level, driving a transition toward spin-polarized metallic or half-metallic behavior accompanied by robust ferromagnetism. Density-of-states and band-structure analyses reveal that magnetism and charge transport in the doped systems are dominated by exchange-split transition-metal 3d states hybridized with N-2p orbitals. Total energy calculations confirm ferromagnetic ground states for both Cr- and Mn-doped ScN, with Mn substitution yielding stronger exchange stabilization and higher magnetic moments. Magnetocrystalline anisotropy energies, evaluated using the force-theorem approach, are found to be negligibly small, indicating weak anisotropy consistent with the moderate spin–orbit coupling strength in ScN-based nitrides. Nevertheless, symmetry breaking around dopant sites gives rise to a finite Dzyaloshinskii–Moriya interaction, leading to weak spin canting and non-collinear magnetic tendencies. The interplay between magnetic exchange coupling, spin–orbit interaction, and local inversion symmetry breaking positions of Cr- and Mn-doped ScN as promising dilute magnetic semiconductors with tunable spin polarization and chiral magnetic interactions, offering a viable platform for nitride-based spintronic and magneto-electronic applications. Full article

Second harmonic (SH) radiation can only be generated in non-centrosymmetric bulk crystals under electric dipole approximation. Nonlinear thin films made from bulk crystals are technologically challenging because of complex and high-temperature fabrication processes. In this work, heterostructures made of two distinct amorphous materials, namely SiO₂ and TiO₂, were prepared through plasma-enhanced atomic layer deposition (PEALD) with deposition temperature of 100 °C. By using the uniaxial dispersion model, we characterized the form birefringence of the deposited films, which can play a crucial role for the phase-matching condition in nonlinear waveguides or other nonlinear optical applications. By applying a fringe-based technique, we determined the largest diagonal component of the effective bulk second-order susceptibility, ${\chi }_{zzz}^{\left(2\right)}$ = 1.30 ± 0.13 pm/V, at a wavelength of 1032 nm. Noteworthy, we observed strong SHG signals from two-component nanolaminates, which are several orders of magnitude larger than those from single layers. The SHG signals from our samples only require the broken inversion symmetry at the interface. Here, optical properties of nanocomposites can be precisely engineered using the promising PEALD technology. Full article

This study investigates the role of silicon (Si) addition in governing the evolution of phase symmetry and microstructural stability in a high-entropy alloy (HEA) synthesized via powder metallurgy. Mechanically alloyed powders were consolidated through conventional sintering, followed by systematic heat treatment to examine symmetry-driven phase transformations. Particular attention is given to the symmetry relationship between body-centered cubic (BCC) and face-centered cubic (FCC) crystal structures and their compositional stabilization mechanisms. X-ray diffraction and microstructural analyses reveal that Si incorporation modifies lattice symmetry, promotes controlled phase transformation, and influences the balance between competing crystallographic phases. The addition of Si contributes to symmetry stabilization by reducing heterogeneity in lattice distortion and suppressing grain coarsening during thermal exposure. These findings demonstrate that compositional tuning can regulate structural symmetry and phase equilibrium in multicomponent alloy systems. The work provides insight into symmetry-controlled material design strategies for enhancing the thermal robustness and structural reliability of HEAs for high-temperature applications. Full article

To develop high-performance iridium phosphorescent complexes, we designed and synthesized a series of iridium phosphorescent complexes (G-1, G-2, B-1, B-2, R-1, R-2) using 3-hydroxy-2-methyl-4-pyrone (maltol, short for mal) and 3-hydroxy-2-ethyl-4-pyrone (ethyl maltol, short for emal) as auxiliary ligands, in combination with 2-phenylpyridine (ppy), 2-(2,4-difluorophenyl)pyridine (dfppy), and 1-phenylisoquinoline (piq) as cyclometalating ligands. We systematically investigated their crystal structures, photophysical behavior, electrochemical properties, and electroluminescent performance. The results revealed that the combination of a pyranone auxiliary ligand with the highly conjugated piq ligand leads to the formation of R-1 and R-2, which possess high molecular symmetry and display favorable photophysical performance. These complexes exhibit solution-phase phosphorescence quantum yields of 64% and 55%, and electroluminescent devices incorporating them reach a maximum external quantum efficiency of 13.4%, with brightness exceeding 13,000 cd/m² and minimal efficiency roll-off. In contrast, complexes incorporating pyridine-based cyclometalating ligands (ppy, dfppy)—G-1, G-2, B-1, and B-2—display weak emission in solution but show enhanced solid-state emission through π–π stacking, with a maximum quantum yield of 25.8%. Density functional theory calculations and electrochemical analysis indicate that the presence of both the pyranone auxiliary ligand and the piq ligand results in optimized frontier orbital energy alignment, enhanced metal-to-ligand charge transfer, and reduced non-radiative transitions, thereby improving emission efficiency. This study provides a theoretical framework and molecular design strategy for the application of pyranone auxiliary ligands in high-performance iridium phosphorescent materials. Full article

Potassium superoxide (KO₂) can form during the oxidation of residual potassium in NaK-contaminated cold traps of sodium-cooled fast reactors. Its strong oxidizing nature, combined with limited thermal stability, raises safety concerns during shutdown and maintenance. Here, we integrate first-principles calculations with experiments to clarify the facet stability, temperature-driven surface evolution, and stepwise thermal decomposition of KO₂. Guided by the tetragonal I4/mmm crystal symmetry of bulk KO₂, symmetry-non-equivalent low-index facets and relevant surface terminations were systematically evaluated to identify physically meaningful exposed surfaces. Ab initio molecular dynamics (AIMD) simulations further show that heating induces progressive surface amorphization and enhanced oxygen mobility, accompanied by the emergence of shortened O-O bonds and outward migration of oxygen species. Kinetic analysis using the climbing-image nudged elastic band (CI-NEB) method indicates that oxygen evolution is preferentially mediated by O₂ release rather than atomic oxygen escape. Differential scanning calorimetry (DSC) reveals two endothermic events consistent with sequential decomposition, while X-ray diffraction (XRD) confirms the transformation of KO₂ into K₂O. Collectively, these results provide an atomistic-to-macroscopic understanding of KO₂ decomposition, offering practical guidance for defining safer preheating windows and handling strategies for NaK-contaminated components. Full article