Structural Transition Research Articles

Transient Structural Transition in Ovonic Threshold Switching Glass

AbstractOvonic threshold switching (OTS), characterized by a rapid resistance drop in chalcogenide glass, has enabled the realization of memory and selectors. Despite over five decades of development, the challenges in characterizing the transient switching in amorphous materials upon reaching the threshold voltage have hindered the establishment of its underlying mechanism. This study uses femtosecond terahertz spectroscopy and ab initio simulation to elucidate the dynamics of the free‐carrier and IR‐active phonons involved in OTS. Specifically, in Te‐rich amorphous GeTe, the generation of transient phonons is observed within picoseconds, a phenomenon associated with an increased Born effective charge due to the alignment of Te‐centered bonds. The findings demonstrate a correlation between the enhancement of polarizability, due to orbital alignment during the disorder–order structural transition while maintaining a macroscopic amorphous structure, and the switching behavior. These results provide valuable insights into the enigmatic OTS phenomenon.

Strain-Induced Antiferroelectric-Ferroelectric-Antiferroelectric Phase Transitions in Epitaxial LaTaO4 Films.

We employed first-principles to delve into the strain-induced structural phase transitions in epitaxial LaTaO4 films. The ground state of bulk LaTaO4 adopts a monoclinic antiferroelectric phase, characterized by the antiphase rotation of two adjacent oxygen octahedra layers. Under epitaxial tensile strain, LaTaO4 thin films undergo a consecutive phase transition, namely, antiferroelectric-ferroelectric-antiferroelectric phase transitions. The ferroelectricity in the orthorhombic phase under tensile strain originates from the in-phase rotation of two adjacent oxygen octahedra layers, in contrast to the case of perovskite systems, in which octahedra rotation suppresses the conventional proper ferroelectricity. With spin-orbit coupling effects, a pronounced Rashba effect at the Brillouin zone center naturally leads to the formation of opposite directions of spin texture. Moreover, the tensile strain also synergistically enhances the corresponding Rashba parameters. Our findings may provide novel insights for controlling oxygen octahedra rotation to achieve control over the ferroelectricity and Rashba effect, which holds promising implications for applications in electronics and spintronics.

Active learning-based automated construction of Hamiltonian for structural phase transitions: a case study on BaTiO3

The effective Hamiltonians have been widely applied to simulate the phase transitions in polarizable materials, with coefficients obtained by fitting to accurate first-principles calculations. However, it is tedious to generate distorted structures with symmetry constraints, in particular when high-ordered terms are considered. In this work, we implement and apply a Bayesian optimization-based approach to sample potential energy surfaces, automating the effective Hamiltonian construction by selecting distorted structures via active learning. Taking BaTiO3(BTO) as an example, we demonstrate that the effective Hamiltonian can be obtained using fewer than 30 distorted structures. Follow-up Monte Carlo simulations can reproduce the structural phase transition temperatures of BTO, comparable to experimental values with an error<10%. Our approach can be straightforwardly applied on other polarizable materials and paves the way for quantitative atomistic modelling of diffusionless phase transitions.

Entropy and Electronic Structure Modulation of a Prussian Blue Analogue Cathode with Suppressed Phase Evolution for Potassium-Ion Batteries.

Severe structural evolution and high content of [Fe(CN)6]4- defects drastically deteriorate K-ion storage performances of Prussian blue-based cathodes. Herein, a potassium manganese iron copper hexacyanoferrate (KFe2/3Mn1/6Cu1/6HCF), with suppressed anionic vacancies, eliminated band gap, and low K-ion diffusion barrier, is regarded as a cathode for potassium-ion batteries. The entropy stabilization effect and robust Cu-N bond induced by the inert Cu-ion with large electronegativity boost KFe2/3Mn1/6Cu1/6HCF to exhibit great phase state stability, thus inhibiting the structural transition of monoclinic ↔ cubic. Hence, KFe2/3Mn1/6Cu1/6HCF undergoes a zero-stress solid-solution reaction mechanism, where Fe and Mn serve as dual active sites for charge compensation. Consequently, KFe2/3Mn1/6Cu1/6HCF displays a high reversible capacity of 127.5 mAh·g-1 with an energy density of 469.2 Wh·kg-1 at 10 mA·g-1 and superior cyclic stability with a high retention of 90.7% over 100 cycles. A high-energy-density K-ion full battery is assembled, contributing an ultralong lifetime over 1000 cycles with a low-capacity fading rate of 0.038% per cycle.

The Role of Protonation in the PfMATE Transporter Protein Structural Transitions.

Multi-antimicrobial extrusion (MATE) transporter membrane proteins provide drug and toxin resistivity by expelling compounds from cells. MATE proteins can be pictured as V-shaped. To regulate its functioning, the protein structure can switch between outward-facing (OF) and inward-facing (IF). Pyrococcus furiosus MATE (PfMATE) is the only member of the multidrug/oligosaccharidyl-lipid/polysaccharide (MOP) superfamily that has available both the IF and OF crystal structures. With the availability of both the IF and OF structures, we are able to perform computational investigations to determine how protonation of specific amino acids causes a cascade of changes in the protein conformation that allow PfMATE to change its state from OF to IF in order to regulate its antiporter function. Using a variety of computational and theoretical techniques, we investigated four different systems of IF and OF PfMATE along with the native archaeal lipid bilayer, without or with protonation at the experimentally determined locations within the protein. We performed molecular dynamics (MD) simulations to investigate the flexibility of the four different PfMATE structures and also performed targeted molecular dynamics (TMD) simulations, during which we observed occluded conformations. Our analysis of hydrogen bond changes, potential of mean force, dynamic network analysis, and transfer entropy analysis provides information on how protonation can induce cascading structural changes responsible for the transition between the IF and OF configurations.

Structural Transition Analysis of Bilayer Black Phosphorus under High Pressure via Ultralow-Frequency Raman Spectroscopy.

The unique anisotropic electron-photon and electron-phonon interactions of black phosphorus (BP) set it apart from other isotropic 2D materials. These anisotropic properties can be adjusted by varying the stacking thickness and sequence as well as by applying external pressure and strain. In contrast to multilayer or bulk BP, the effects of pressure on bilayer BP are still not fully elucidated. This study presents experimental evidence that explores the high-pressure response (0-20 GPa) of bilayer BP within the extreme low Raman shift region (5-150 cm-1), aiming at verifying structural phase transitions and stacking sequence variations. Notably, phase transitions were observed at ∼7 GPa for the orthorhombic to rhombohedral transition and at ∼14-16 GPa for a further transition to a simple cubic structure. The effects of pressure on bilayer BP with three distinct stacking sequences (AA, AB, and AC) were analyzed using angular-resolved polarized Raman spectroscopy (ARPR). The recovery of all characteristic Raman modes after the application of pressure substantiates the reversibility of the structural phase transitions in bilayer BP across all three stacking sequences. However, significant alterations in the stacking sequences were observed before and after the application of hydrostatic pressure. Specifically, AA and AC stacking sequences showed a tendency to relax into an optimized interlayer AB stacking structure upon the release of pressure from 20 to 0 GPa. This observed change in the stacking sequences of bilayer BP under pressure is detected for the first time in this work. The pressure-induced modifications in the stacking sequences, and consequently in the anisotropic properties of bilayer BP, highlight its potential as a promising material for pressure- (or strain-) sensitive optoelectronic nanodevices. Additionally, this study offers novel insights into the analysis of anisotropic interlayer interactions in other van der Waals-stacked 2D materials.

Broad-angle coherent perfect absorption-lasing and collimation in two-dimensional non-Hermitian phononic crystals

Abstract Coherent perfect absorption-lasing and collimation have been extensively studied primarily for normal incidence, leaving broad-angle scenarios relatively unexplored. In this work, we investigate a two-dimensional non-Hermitian phononic crystal, aiming to achieve broad-angle coherent perfect absorption-lasing and collimation. Our approach involves orchestrating a parity-time phase transition in the band structure through a combination of non-symmorphic glide symmetry in the lattice, gain-loss modulation, and engineering of the band structure. In both the real and imaginary parts of the band structure, exceptional points form a slab-like contour with nearly zero dispersion along the boundary of the Brillouin zone. As a result, the range of incidence angles for coherent perfect absorption-lasing and collimation is significantly expanded at the frequency of the exceptional points.

Pattern formations and their active manipulation in a Rydberg noisy-dressed Bose-Einstein condensate.

We investigate the formation and manipulation of spatial patterns and their structural phase transitions by examining the effects of laser linewidth on the dynamics of Rydberg noise-dressed Bose-Einstein condensates (RnD BECs). We discover that the homogeneous matter wave can transition into various types of self-organized patterns, which are manipulated by tuning the laser linewidth, control field intensity, and atomic density. Remarkably, the system exhibits stable nonlocal matter-wave solitons, vortices, and soliton molecules under specific laser linewidths.

Bonding states underpinning structural transitions in IrTe2 observed with micro-ARPES

Competing interactions in low-dimensional materials can produce nearly degenerate electronic and structural phases. We investigate structural phase transitions in layered IrTe2 for which a number of potential transition mechanisms have been postulated. The spatial coexistence of multiple phases on the micron scale has prevented a detailed analysis of the electronic structure. By exploiting micro-angle-resolved photoemission spectroscopy obtained with synchrotron radiation we extract the electronic structure of the multiple structural phases in IrTe2 in order to address the mechanism underlying the phase transitions. We find direct evidence of lowered energy states that appear in the low-temperature phases, states previously predicted by calculations and extended here. Our results validate a proposed scenario of bonding and antibonding states as the driver of the phase transitions. Published by the American Physical Society 2024

Charge transfer induced phase transition in Li2MnO3 at high pressure

Efficient and better energy storage materials are of utmost technological importance to reduce energy dependence on the fossil fuels. Li2MnO3is one such material having potential to meet most of the requirements for energy storage. This material has been synthesized using solid state synthesis route. High pressure structural and vibrational studies on this material have been carried out upto ∼22 and 26 GPa respectively. These investigations show occurrence of a hitherto unknown second order phase transition to a new low symmetry phase whose symmetry is constrained to be monoclinic with space group P21/n at pressure of ∼2.3 GPa in Li2MnO3. The bulk modulus and its derivative determined by fitting theP-Vdata with third order Birch-Murnaghan equation of state are 113.3 ± 13.1 GPa and 4.1 ± 1.2 respectively. Mode Grüneisen parameter calculated for all the Raman modes show positive values which indicates the absence of any soft mode in this material. A microscopic mechanism based on bond-charge transfer is invoked and applied to understand the spectroscopic changes occurring in this material which also manifests second order structural phase transition. Enhancement in covalent character of Li-O bonds in the Li-O polyhedra is inferred based on the spectroscopic observation and above mechanism.

Exploring the phase composition and crystal structure of potassium-doped copper sulfide

This study investigates the phase composition, crystal structure, and phase transitions of potassium-substituted copper sulfide (KxCu1.97-xS), focusing on the effects of potassium doping on the material’s properties. Using X-ray diffraction analysis, we identified the structural characteristics of potassium-doped variants, confirming their retention of the monoclinic chalcocite structure (P21/c) with slight modifications in lattice parameters. The incorporation of potassium ions resulted in observable changes in the unit cell dimensions, suggesting enhanced ionic interactions and potential impacts on electronic conductivity. The thermoelectric coefficient, electro-conductivity, and thermoelectric power were also examined, revealing that potassium doping could stabilize certain phases under varying temperature conditions. This work provides valuable insights into the structure-property relationships in copper sulfides, highlighting the potential for tailored materials in thermoelectric applications and other advanced technologies. Future studies will explore the implications of these findings for optimizing the performance of potassium-doped copper sulfides in practical applications.

Evaluation of Structural Transition Joints Cu-Al-AlMg3 Used in Galvanizer Hangers

The paper deals with the evaluation of the quality of Cu-Al-AlMg3 structural transition joints (STJ) made by explosion welding proposed for the renovation of galvanizer hangers. The three-layer joint consisted of electrolytic copper with a thickness of 25 mm, 2 mm of aluminium represented by the AW1050 alloy, and 25 mm of the EN AW 575 aluminium alloy. Light microscopy analysis confirmed the wavy pattern of both interfaces of the welded joint and significant plastic deformation in close proximity to the waves. Microhardness measurement revealed a partial strain hardening of the AW5754 copper-aluminium alloy near the interface and a significant increase in microhardness in the vortex zone of waves, reaching a value of up to 863 HV 0.025. Microcracks were also observed in these places. The intermetallic phase Al2Cu was identified in the vortex zones by XRD analysis. As a continuous layer of intermetallic phase was not observed in the interface of the welded joint, it is possible to consider the used welding parameters as appropriate. A semi-quantitative EDX analysis revealed a diversity of chemical composition in the vortex zones, which does not correspond to the phase composition based on the equilibrium binary Al-Cu diagram due to non-equilibrium conditions in the formation of the welded joint interface. The bond strength of three-layer welded joint evaluated by the strength test ranged from 151 to 171 MPa, which represented approximately a two-fold increase in comparison to the ultimate tensile strength of alloy AW1050, while the failure occurred in all samples at the AW1050-AW5754 alloy interface.

1H and 13C NMR and FTIR Spectroscopic Analysis of Formic Acid Dissociation Dynamics in Water.

The formation and transport of ionic charges in formic acid-water (HCOOH-H2O) mixtures with initial water mole fractions ranging from XH2Oi = 0 to 1 were investigated using 13C and 1H NMR, FTIR spectroscopy, viscosity, conductivity, and pH measurements. The maximum molar concentration of ions (H3O+ and HCOO-), along with the relative differences between theoretical and experimental densities, spin-lattice relaxation times (T1), activation energies (Ea), viscosity (η), and conductivity (σ), were identified within the range of XH2Oi ≈ 0.5-0.7. These results indicate that pure formic acid (FA) solutions predominantly consist of cyclic dimers at room temperature. As the water mole fraction increases up to 0.6, a structural shift occurs from cyclic dimers to a mixture of linear and cyclic dimers, driven by the formation of strong hydrogen bonds. Beyond a water mole fraction of 0.6, the structure transitions to linear dimers, with FA molecules behaving as free entities in the water. Furthermore, the acidity was found to increase approximately 2-fold with every 0.1 increment in water mole fraction. These findings are critical for understanding the kinetics of formic acid anions in body fluids, the structure of the hydrogen bonding network, and ionization energies.

Reversible Single-Crystal to Single-Crystal Transformation and Associated Magnetism of a Cyanide-Bridged Chiral-Structured Magnet.

A chiral molecule-based magnet [MnII (S-pnH) (H2O)][MnIII(CN)6]·H2O (S-pn = S-1,2-diaminopropane), 1S·2H2O (P212121), has been obtained, which has a two-dimensional (2D) square network of cyanide-bridged MnII-MnIII ions. The crystallographic research on this coordination polymer indicates that it is robust enough to transform the single-crystal structure upon dehydration as well as rehydration. Meanwhile, the magnetic property changes are reversibly associated with the structural phase transitions. The complete reversibility upon dehydration/rehydration was demonstrated using in situ X-ray diffraction from the as-prepared 1S·2H2O to the dehydrated [MnII (S-pnH)][MnIII(CN)6], 1S, then rehydrated to [MnII (S-pnH) (H2O)][MnIII(CN)6]·H2O, 1S-HP, and dehydrated again to [MnII (S-pnH)][MnIII(CN)6], 1S-DeHP. Neither the space groups nor the crystal axes changed during the dehydration/rehydration process. The dehydration is considered to be associated with a change in the coordination of the S-pnH from one 2D layer to the neighboring one involving a proton transfer and is accompanied by new cyanide bridging of MnII and MnIII ions formed between the 2D sheet. Corresponding to the 2D to three-dimensional (3D) structural transition, the study of magnetic properties reveals that the Curie temperature of long-range magnetic ordering for 1S (TC = 45 K) is more than double that for 1S·2H2O (TC = 21 K).

The role of surface substitution in the atomic disorder-to-order phase transition in multi-component core-shell structures.

Intermetallic phases with atomic ordering are highly active and stable in catalysts. However, understanding the atomistic mechanisms of disorder-to-order phase transition, particularly in multi-component systems, remains challenging. Here, we investigate the atom diffusion and phase transition within Pd@Pt-Co cubic nanoparticles during annealing, using in-situ electron microscopy and ex-situ atomic resolution element analysis. We reveal that initial outward diffusing Pd partially substitutes Pt, forming a (Pt, Pd)-Co ternary system in the surface region, enabling the phase transition at a low temperature of 400 °C, followed by shape-preserved inward propagation of the ordered phase. At higher temperatures, excessive interdiffusion across the interface changes the stoichiometric ratio, diminishing the atomic ordering, leading to obvious change in morphology. Calculations indicate that the Pd-substitute in (Pt, Pd)-Co system leads to a significantly lower phase transition temperature compared to that of Pt-Co alloy and thus a lower activation energy for atomic diffusion. These insights into atomistic behavior are crucial for future design of multi-component systems.

Room Temperature Phase Transition and Luminescence Behavior of a Novel Metal‐Free Ionic Crystal [C7H16NO][ClO4

AbstractMetal‐free ionic crystals have attracted tremendous attention for their environmental friendliness, biocompatibility, easy fabrication and structural variability. Herein, a metal‐free ionic crystal [C7H16NO][ClO4] ([C7H16NO]=1‐methyl‐4‐piperidinemethanol) with a dielectric transition at room temperature was designed and constructed. Differential scanning calorimetry (DSC) proved that there exists a reversible phase transition near room temperature at 304 K, accompanied with switchable dielectric behaviors between the low and high dielectric states. The single crystal structure show that the mechanism of such structural phase transition mainly results from the dynamic motion of perchlorate anions. The compound is further shown to exhibit remarkable luminescent properties, characterized by a prolonged lifetime of 18.6 ns. This work offers valuable insights into the construction of room temperature phase‐transition ionic crystals involved with dielectric switching and blue luminescence properties.

Pressure induced semiconductor-like to metal transition and linear magnetoresistance in Cr2S2.88 single crystal.

The transition metal chalcogenide Cr2S3-x has unique properties, such as a lower antiferromagnetic transition temperature, semiconducting behavior, and thermoelectric properties. We focus on the effects of high pressure on the properties of electrical transport and structure in the single crystal Cr2S2.88. It is observed that the resistance drops abruptly by approximately two orders of magnitude and the temperature derivative of the resistance changes from negative to positive after 15.7 GPa. The Cr2S2.88 crystal has undergone transitions from a semiconductor-like phase to a metal I phase and then to another metal II phase. Simultaneously, a structural phase transition after 16.1 GPa is confirmed by synchrotron angle dispersive X-ray diffraction (AD-XRD). After the structural phase transition, the negative magnetoresistance becomes positive with increasing pressure and shows a linear relationship in the metal II phase. Electron-type carriers dominate in the semiconductor-like phase, but hole-type carriers dominate after the structural phase transition. Our work provides an example of the effective modulation of semiconductor-like properties by pressure, which is meaningful for the innovation and development of semiconductor technology.

Polymorphism in Type-II Dirac Semimetal WSi2 under Pressure: Structural, Mechanical, and Electronic Insights.

The type-II Dirac candidate semimetal WSi2 is a promising candidate for electronic devices, quantum computing, and topological materials research, owing its distinct electronic structure and superior mechanical properties. Here, we synthesized high-quality WSi2 materials and systematically investigated their compressive behavior, and structural and electronic properties under high pressure using in-situ high pressure experiments, complemented by first-principles calculations. The results confirms that WSi2 has the properties of a type-II Dirac semimetal. Our results demonstrate that WSi2 maintains structural stability under high pressure but undergoes an electronic phase transition from a semimetal to a metal around 40 GPa. Additionally, the mechanical hardness softens discontinuously at this pressure. The structural stability of WSi2 under high pressure is attributed to the strong hybridization of Si-3p and W-5d electrons, the rigid crystal lattice, and the adaptable electronic structure. The pressure-induced electronic phase transition and softening are primarily governed by the energy band reconstruction and W-5d orbitals. This study provides valuable insights into the high-pressure behavior of type-II Dirac semimetal, highlighting their potential for advanced applications in electronic devices and topological quantum computing under extreme conditions by elucidating their structural stability and electronic phase transition mechanisms.

Understanding melting behavior of aluminum clusters using machine learned deep neural network potential energy surfaces.

Deep neural network-based deep potentials (DP), developed by Tuo et al., have been used to compute the thermodynamic properties of free aluminum clusters with accuracy close to that of density functional theory. Although Jarrold and collaborators have reported extensive experimental measurements on the melting temperatures and heat capacities of free aluminum clusters, no reports exist for finite-temperature abinitio simulations on larger clusters (N > 55 atoms). We report the heat capacities and melting temperatures for 32 clusters in the size range of 48-342 atoms, computed using the multiple histogram technique. Extensive molecular dynamics (MD) simulations at twenty four temperatures have been performed for all the clusters. Our results are in very good agreement with the experimental melting temperatures for 19 clusters. Except for a few sizes, the interesting features in the heat capacities have been reproduced. To gain insight into the striking features reported in the experiments, we used structural and dynamical descriptors such as temperature-dependent mean squared displacements and the Lindemann index. Bimodal features observed in Al116 and the weak shoulder seen in Al52 are attributed to solid-solid structural transitions. In confirmation of the earlier reports, we observe that the behavior of the heat capacities is significantly influenced by the nature of the ground state geometries. Our findings show that the sharp drop in the melting temperature of the 56-atom cluster is a consequence of the change in the geometry of Al55. Mulliken population analysis of Al55 reveals that the charge-induced local electric field is responsible for the strong bonding between core and surface atoms, leading to the higher melting temperature. Our calculations do not support the lower melting temperature observed in experimental studies of Al69. Our results indicate that Al48 is in a liquid state above 600K and does not support the high melting temperature reported in the experiment. It turns out that the accuracy of the DP model by Tuo et al. is not reliable for MD simulations beyond 750K. We also report low-lying equilibrium geometries and thermodynamics of 11 larger clusters (N = 147-342) that have not been previously reported, and the melting temperatures of these clusters are in good agreement with the experimental ones.

Strain Programming of Oxygen Octahedral Symmetry in Perovskite Oxide Thin Films

AbstractThe collective rotations of oxygen octahedra play an important role in determining the physical properties of functional perovskite oxides. The epitaxial strain can serve as an effective means to modify the oxygen octahedral symmetry (OOS), i.e., oxygen octahedral rotation or tilt (OOR/OOT). However, the strain‐OOS coupling that may alter the details of the OOS, thereby the physical properties, has not been fully understood. In this work, it is demonstrated that epitaxial strain can not only induce a structural phase transition but also precisely tune the degree of OOR. The correlated metal CaNbO3, which is orthorhombic, is studied by growing as epitaxial thin films. By imposing epitaxial strain, it is found that the film undergoes a structural phase transition from orthorhombic to tetragonal upon fully straining (i.e., from a+b−b− to a0a0c−). In unstrained films, the octahedral rotation along the c‐axis is as large as 15.7° that can be tuned to 6.6° by strain. This finding offers a general approach to manipulating OOR/OOT via strain engineering in complex oxide heterostructures.