Consecutive Phase Transitions Research Articles

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.

Effect of Y3+ doping of rare earth element on microstructure and antiferromagnetism of CuFeO2 ceramics

In this work, a set of CuFe1-xYxO2 (x = 0–0.02) specimens were synthesized using the conventional high-temperature solid-state reaction method, and the impact of Y3+ doping on the microstructure and magnetic properties of CuFeO2 ceramics was investigated. The introduction of Y3+ ions in place of Fe3+ ions induced alterations in the microstructure of CuFeO2, leading to lattice distortion. X-ray diffraction analysis confirmed the presence of impurity phases in the CuFe1-xYxO2 series samples at high doping concentrations (x ≥ 0.015). In contrast, low doping concentrations (x ≤ 0.0125) exhibited a singular copper-iron ore structure. The microstructures of the ceramic samples were examined using SEM, findings suggest that the presence of high concentrations of dopants hinders the formation of ceramic samples with high density. XPS analysis reveals that the introduction of a low concentration of Y3+ dopant does not impact the oxidation state of Cu and Fe. Raman spectroscopy results indicate that the doping process weakens the vibration mode of CuFe1-xYxO2 ceramic samples. Additionally, measurements conducted using the PPMS demonstrate that the serial samples undergo two consecutive magnetic phase transitions at temperatures of 16K and 11K. The magnetization versus M − H curve of the doped sample exhibits both antiferromagnetic and ferromagnetic behavior. The increase in magnetic susceptibility can be attributed to the greater magnetic moment of doped Y3+ compared to Fe3+. Consequently, the magnetic transformation of the sample is influenced by various factors, including lattice distortion, alterations in ion valence states, variations in microscopic defect types, and modifications in magnetic interactions.

Two-well linearization for solid-solid phase transitions

In this paper we consider nonlinearly elastic, frame-indifferent, and singularly perturbed two-well models for materials undergoing solid-solid phase transitions in any space dimensions, and we perform a simultaneous passage to sharp-interface and small-strain limits. Sequences of deformations with equibounded energies are decomposed via suitable Caccioppoli partitions into the sum of piecewise constant rigid movements and suitably rescaled displacements. These converge to limiting partitions, deformations, and displacements, respectively. Whereas limiting deformations are simple laminates whose gradients only attain two values, the limiting displacements belong to the class of special functions with bounded variation ( SBV ). The latter feature elastic contributions measuring the distance to simple laminates, as well as jumps associated to two consecutive phase transitions having vanishing distance, and thus undetected by the limiting deformations. By \Gamma - convergence we identify an effective limiting model given by the sum of a quadratic linearized elastic energy in terms of displacements along with two surface terms. The first one is proportional to the total length of interfaces created by jumps in the gradient of the limiting deformation. The second one is proportional to twice the total length of interfaces created by jumps in the limiting displacement, as well as by the boundaries of limiting partitions. A main tool of our analysis is a novel two-well rigidity estimate which has been derived in [Calc. Var. Partial Differential Equations 59, art. 44 (2020)] for a model with anisotropic second-order perturbation.

Ultrasonic investigation of the elastic properties of the approximant GdCd6

We have investigated complementarily the magneto-elastic coupling in the approximant GdCd6 by measuring the temperature and magnetic field dependence of the longitudinal elastic constant C11. A pronounced elastic softening toward the phase transition temperature Ts= 156 K was observed in the temperature dependence of the C11, suggesting the presence of a structural phase transition. Furthermore, anomalous elastic behavior was observed in the temperature dependence of the C11 below 20 K, closely related to the already known consecutive magnetic phase transitions. The H–T magnetic phase diagram deduced from elastic anomalies appearing at the different phase transitions are consistent with our previous data of the other independent elastic constants CE= (C11−C12)/2 and C44 for a cubic crystal. We argue the origin of the structural phase transition and low temperature elastic property including a possible origin of such a rich variety of magnetic phases.

Chemically Fueled Autonomous Sol→Gel→Sol→Gel→Sol Transitions.

Complex non-equilibrium phase behaviors are a hallmark of natural self-assembling systems. Here we show how intricate phase transitions can be achieved through a chemically fueled reaction cycle to yield autonomous sol→gel→sol→gel→sol transitions. A relay of chemical transformations based on thiazinane metathesis leads to two consecutive transient gelations in a closed system. Within seconds of fuel addition to deactivated thiazinane monomers, an imine-based hydrogel forms that consists of fibrillar microspheres. This gel quickly loses its mechanical strength and forms a solution, from which a second aldehyde-based gel nucleates and remains stable for over one day. Overall, our reaction cycle gives rise to two consecutive re-entrant phase transitions without any experimental intervention.

Topological phase transitions without symmetry indication in NaZnSb_{1-x}Bi_x

We study topological phase transitions in tetragonal NaZnSb_{1-x}Bi_x, driven by the chemical composition x. Notably, we examine mirror Chern numbers that change without symmetry indicators. First-principles calculations are performed to show that NaZnSb_{1-x}Bi_x experiences consecutive topological phase transitions, diagnosed by the strong {mathbb {Z}}_2 topological index nu _{0} and two mirror Chern numbers mu _{x} and mu _{xy}. As the chemical composition x increases, the topological invariants (mu _{x}mu _{xy}nu _{0}) change from (000), (020), (220), to (111) at x = 0.15, 0.20, and 0.53, respectively. A simplified low-energy effective model is developed to examine the mirror Chern number changes, highlighting the central role of spectator Dirac fermions in avoiding symmetry indicators. Our findings suggest that NaZnSb_{1-x}Bi_{x} can be an exciting testbed for exploring the interplay between the topology and symmetry.

Simple Visualization of Universal Ferroelastic Domain Walls in Lead Halide Perovskites.

Domain features and domain walls in lead halide perovskites (LHPs) have attracted broad interest due to their potential impact on optoelectronic properties of this unique class of solution-processable semiconductors. Using nonpolarized light and simple imaging configurations, ferroelastic twin domains and their switchings through multiple consecutive phase transitions are directly visualized. This direct optical contrast originates from finite optical reflections at the wall interface between two compositionally identical, orientationally different, optically anisotropic domains inside the material bulk. The findings show these domain walls serve as internal reflectors and steer energy transport inside halide perovskites optically. First-principles calculations show universal low domain-wall energies and modest energy barriers of domain switching, confirming their prevalent appearance, stable presence, and facile moving observed in the experiments. The generality of ferroelasticity in halide perovskites stems from their soft bonding characteristics. This work shows the feasibility of using LHP twin domain walls as optical guides of internal photoexcitations, capable of nonvolatile on-off switching and tunable positioning endowed by their universal ferroelasticity.

Differences of the temperatures of ferroelectric and magnetic phase transitions of perovskites

Binary and ternary AB′0.5 B″0.5O3 oxides with a complex perovskite structure, possessing the consecutive ferroelectric or antiferroelectric phase transitions at T C and ferromagnetic, antiferromagnetic, or ferrimagnetic phase transitions at T N, are considered together with classical ferroelectrics and antiferroelectrics. The common correlations between these temperatures, their differences T С-T N and interatomic bond A-O (δ AO) or B-O (δ BO) strains are revealed. Some common correlations between their temperatures T С, T N, T С-T N differences, and δ AO or δ BO are revealed. It is established that these differences for multiferroics are in common dependences with classical ferroelectrics and antiferroelectrics.

Consecutive topological phase transitions and colossal magnetoresistance in a magnetic topological semimetal

The combination of magnetic symmetries and electronic band topology provides a promising route for realizing topologically nontrivial quasiparticles, and the manipulation of magnetic structures may enable the switching between topological phases, with the potential for achieving functional physical properties. Here, we report measurements of the electrical resistivity of EuCd2As2 under pressure, which show an intriguing insulating dome at pressures between pc1 ~ 1.0 GPa and pc2 ~ 2.0 GPa, situated between two regimes with metallic transport. The insulating state can be fully suppressed by a small magnetic field, leading to a colossal negative magnetoresistance on the order of 105%, accessible via a modest field of ~ 0.2 T. First-principles calculations reveal that the dramatic evolution of the resistivity under pressure can be attributed to consecutive transitions of EuCd2As2 from a magnetic topological insulator to a trivial insulator, and then to a Weyl semimetal, with the latter resulting from a pressure-induced change in the magnetic ground state. Similarly, the colossal magnetoresistance results from a field-induced polarization of the magnetic moments, transforming EuCd2As2 from a trivial insulator to a Weyl semimetal. These findings underscore weak exchange couplings and weak magnetic anisotropy as ingredients for discovering tunable magnetic topological materials with desirable functionalities.

Orthorhombic charge density wave on the tetragonal lattice of EuAl4.

EuAl4 possesses the BaAl4 crystal structure type with tetragonal symmetry I4/mmm. It undergoes a charge density wave (CDW) transition at T CDW= 145 K and features four consecutive antiferromagnetic phase transitions below 16 K. Here we use single-crystal X-ray diffraction to determine the incommensurately modulated crystal structure of EuAl4 in its CDW state. The CDW is shown to be incommensurate with modulation wave vector q= (0,0,0.1781 (3)) at 70 K. The symmetry of the incommensurately modulated crystal structure is orthorhombic with superspace group Fmmm(00σ)s00, where Fmmm is a subgroup of I4/mmm of index 2. Both the lattice and the atomic coordinates of the basic structure remain tetragonal. Symmetry breaking is entirely due to the modulation wave, where atoms Eu and Al1 have displacements exclusively along a, while the fourfold rotation would require equal displacement amplitudes along a and b. The calculated band structure of the basic structure and interatomic distances in the modulated crystal structure both indicate the Al atoms as the location of the CDW. The tem-per-ature dependence of the specific heat reveals an anomaly at T CDW= 145 K of a magnitude similar to canonical CDW systems. The present discovery of orthorhombic symmetry for the CDW state of EuAl4 leads to the suggestion of monoclinic instead of orthorhombic symmetry for the third AFM state.

Crystallization from Sodium Sulphate Solution Confined in Red Clay Brick during Temperature Decrease

Water with dissolved contaminations is a frequent problem faced in porous building materials such as masonry, or cement-based composites. It regards both contemporary constructions, and those belonging to the cultural heritage. Among soluble salts, sodium sulfate is recognized as one of the most dangerous one. Since crystals of Na2SO4 can occur in the variety of forms, its crystallization in pores of a building material is a challenging and not fully recognized issue. The main object of the presented research is to identify the consecutive phase transitions occurring within red clay brick containing sodium sulphate solution during cooling. The first stage of an experimental investigation was performed by means of mercury intrusion porosimetry to verify whether cyclic crystallization has a damaging effect on material microstructure. In the second step of experimental analysis differential scanning calorimetry was applied. The technique was used to monitor the crystallization of sodium sulphate confined in samples during repeating cooling-heating cycles covering temperature range from -20°C to 40°C. It was observed that during primary crystallization, sodium sulfate heptahydrate is the first precipitating phase and the transition begins far below its equilibrium temperature. Subsequently, the heptahydrate transforms into mirabilite, which probably induced rapid ice crystallization. Nevertheless, if decahydrate nuclei are provided in pore solution, sodium sulphate precipitates directly as mirabilite with no heptahydrate formation. Such a pattern is observed for both analysed solution concentration, i.e. 25% and 30%.

XY model with competing higher-order interactions.

We study effects of competing pairwise higher-order interactions (HOI) with alternating signs and exponentially decreasing intensity on critical behavior of the XY model. It is found that critical properties of such a generalized model can be very different from the standard XY model and can strongly depend on whether the number of HOI terms is odd or even. Inclusion of any odd number of HOI terms results in two consecutive phase transitions to distinct ferromagnetic quasi-long-range order phases. Even number of HOI terms leads to two phase transitions only if the decay of the HOI intensities is relatively slow. Then the high-temperature transition to the ferromagnetic phase is followed by another transition to a peculiar competition-induced canted ferromagnetic phase. In the limit of an infinite number of HOI terms only one phase transition is confirmed, and under the conditions of fierce competition between the even and odd terms the transition temperature can be suppressed practically to zero.

Polymorphic Ga2S3 nanowires: phase-controlled growth and crystal structure calculations.

The polymorphism of nanostructures is of paramount importance for many promising applications in high-performance nanodevices. We report the chemical vapor deposition synthesis of Ga2S3 nanowires (NWs) that show the consecutive phase transitions of monoclinic (M) → hexagonal (H) → wurtzite (W) → zinc blende (C) when lowering the growth temperature from 850 to 600 °C. At the highest temperature, single-crystalline NWs were grown in the thermodynamically stable M phase. Two types of H phase exhibited 1.8 nm periodic superlattice structures owing to the distinctively ordered Ga sites. They consisted of three rotational variants of the M phase along the growth direction ([001]M = [0001]H/W) but with different sequences in the variants. The phases shared the same crystallographic axis within the NWs, producing novel core–shell structures to illustrate the phase evolution. The relative stabilities of these phases were predicted using density functional theory calculations, and the results support the successive phase evolution. Photodetector devices based on the p-type M and H phase Ga2S3 NWs showed excellent UV photoresponse performance.

Unconventional Thermal and Magnetic-Field-Driven Changes of a Bipartite Entanglement of a Mixed Spin-(1/2,S) Heisenberg Dimer with an Uniaxial Single-Ion Anisotropy.

The concept of negativity is adapted in order to explore the quantum and thermal entanglement of the mixed spin-(1/2,S) Heisenberg dimers in presence of an external magnetic field. The mutual interplay between the spin size S, XXZ exchange and uniaxial single-ion anisotropy is thoroughly examined with a goal to tune the degree and thermal stability of the pairwise entanglement. It turns out that the antiferromagnetic spin-(1/2,S) Heisenberg dimers exhibit higher degree of entanglement and higher threshold temperature in comparison with their ferromagnetic counterparts when assuming the same set of model parameters. The increasing spin magnitude S accompanied with an easy-plane uniaxial single-ion anisotropy can enhance not only the thermal stability but simultaneously the degree of entanglement. It is additionally shown that the further enhancement of a bipartite entanglement can be achieved in the mixed spin-(1/2,S) Heisenberg dimers, involving half-odd-integer spins S. Under this condition the thermal negativity saturates at low-enough temperatures in its maximal value regardless of the magnitude of half-odd-integer spin S. The magnetic field induces consecutive discontinuous phase transitions in the mixed spin-(1/2,S) Heisenberg dimers with , which are manifested in a surprising oscillating magnetic-field dependence of the negativity observed at low enough temperature.

Structural phase transition and amorphization in hexagonal SiC subjected to dynamic loading

Understanding the dynamic behavior of silicon carbide (SiC) at extreme conditions is critical for applications such as coatings and armor. Revealing the plasticity and phase transition in SiC under intensive dynamic loading is among the key concerns. However, the effects of polytypes in SiC as well as the various loading conditions on its dynamic material responses are still not well understood. Here we carry out a series of large-scale molecular dynamics (MD) simulations to explore the inelastic responses of hexagonal SiC subjected to shock and ramp compression along the [0001] direction. The shock responses present three regimes sequentially as the shock particle velocity is increased from 0.5 km/s to 6 km/s: a single elastic wave, a multi-wave structure consisting of an elastic-plastic wave followed by two consecutive phase transition waves, and finally, an overdriven structural phase transformation wave. The original wurtzite structure is observed to transform into a 6-coordinated rock salt structure through a 5-coordinated intermediate structure. Furthermore, slip along the <112‾0> direction on the (0001) plane causes multiple stacking faults and amorphization when subjected to intense shock compression. The effects of temperature and strain rate on the material responses of hexagonal SiC are decoupled by performing ramp loading simulations. The results reveal that a lower temperature rise impedes atomic motion while a lower strain rate promotes it, highlighting a competitive effect. Besides, due to the limited availability of slip planes, dynamic compression can lead to the formation of nanograins in hexagonal SiC, and nanograins refinement with increasing shock intensity is observed. These results provide important insights into the deformation of SiC polytypes under extreme conditions and promote the understanding of the dynamic properties of hexagonal structure covalent materials.

Topological phase transitions and a spin-related metallic state in inverted HgTe quantum wells under in-plane magnetic field

We show that in inverted HgTe quantum wells, the application of a strong in-plane magnetic field restores the normal sequence of the subbands, thus transforming the system from a topological insulator into a normal insulator phase. The transformation consists of two consecutive quantum phase transitions due to the large Zeeman splitting of electron states. On the other hand, due to the negligible Zeeman splitting of hole states, the intermediate phase between the transitions is semimetallic. Both phase transitions and the semimetallic phase have already been observed, and our theory allows for a consistent interpretation of the experimental results.

Determination of the Crystal Structures in the A-Site-Ordered YBaMn2O6 Perovskite

We present a complete structural study of the successive phase transitions observed in the YBaMn2O6 compound with the layered ordering of cations on the perovskite A-site. We have combined synchrotron radiation X-ray powder diffraction and symmetry-adapted mode analysis to describe the distorted structures as pseudosymmetric with respect to the parent tetragonal structure. The YBaMn2O6 compound shows three consecutive phase transitions on cooling from 603 K down to 100 K. It undergoes a first-order structural transition at T1 ≈ 512 K from a C2/m cell with a single Mn site to a P21/c cell with two nonequivalent Mn sites. No checkerboard ordering of the two types of MnO6 octahedra is revealed, and there is no significant charge segregation. A second transition is observed below T2 ≈ 460 K giving rise to a duplication of the c-axis and the occurrence of four nonequivalent Mn sites. These sites are grouped in two pairs, producing, in this case, a checkerboard arrangement in the ab-plane with an average charge segregation of Δq ≈ 0.4 e–. The observed distortions in this phase disagree with the formation of an orbital-ordered phase. Finally, another structural transition is observed coupled to the magnetic transition at TN ≈ 200 K and the c-axis is no longer duplicated. The low-temperature phase is polar with SG P21. It also contains four nonequivalent Mn sites grouped in two pairs. The charge difference between these pairs is increased, achieving a value of Δq ≈ 0.7 e–. In this phase, an asymmetric stretching mode favors a Jahn–Teller-like distortion in the expanded MnO6 octahedra that could be associated with an ordering of eg (3dx2–z2/3dy2–z2) orbitals. Our refinements disclose that this phase is ferroelectric with significant polar displacements of the Mn and Obasal atoms along the b-axis. The simultaneous occurrence of ferroelectricity and magnetic ordering indicates that YBaMn2O6 can be considered as a type II multiferroic compound and can present magnetoelectric coupling.

Effects of a pestilent species on the stability of cyclically dominant species

Cyclic dominance is frequently believed to be a mechanism that maintains diversity of competing species. But this delicate balance could also be fragile if some of the members is weakened because an extinction of a species will involve the annihilation of its predator hence leaving only a single species alive. To check this expectation we here introduce a fourth species which chases exclusively a single member of the basic model composed by three cyclically dominant species. Interestingly, the coexistence is not necessarily broken and we have detected three consecutive phase transitions as we vary only the invasion strength of the fourth pestilent species. The resulting phases are analyzed by different techniques including the study of the Hamming distance density profiles. Some of our observations strengthen previous findings about cyclically dominant system, but they also offer new revelations and counter-intuitive phenomenon, like supporting pestilent species may result in its extinction, hence enriching our understanding about these very simple but still surprisingly complex systems.

Evolution of topological defects at two sequential phase transitions of Nd2SrFe2O7

How topological defects, unavoidable at symmetry-breaking phase transitions in a wide range of systems, evolve through consecutive phase transitions with different broken symmetries remains unexplored. Nd2SrFe2O7, a bilayer ferrite, exhibits two intriguing structural phase transitions and dense networks of the so-called type-II Z8 structural vortices at room temperature, so it is an ideal system to explore the topological defect evolution. From our extensive experimental investigation, we demonstrate that the cooling rate at the second-order transition (1290oC) plays a decisive role in determining the vortex density at room temperature, following the universal Kibble-Zurek mechanism. In addition, we discovered a transformation between topologically-distinct vortices (Z8 to Z4 vortices) at the first-order transition (550oC), which conserves the number of vortex cores. Remarkably, the Z4 vortices consist of two phases with an identical symmetry but two distinct magnitudes of an order parameter. Furthermore, when lattice distortion is enhanced by chemical doping, a new type of topological defects emerges: loop domain walls with orthorhombic distortions in the tetragonal background, resulting in unique pseudo-orthorhombic twins. Our findings open a new avenue to explore the evolution of topological defects through multiple phase transitions.

A P3-Type K1/2Mn5/6Mg1/12Ni1/12O2 Cathode Material for Potassium-Ion Batteries with High Structural Reversibility Secured by the Mg-Ni Pinning Effect.

Mn-based layered oxides are very attractive as cathodes for potassium-ion batteries (PIBs) due to their low-cost and environmentally friendly precursors. Their transfer to practical application, however, is inhibited by some issues including consecutive phase transitions, sluggish K+ deintercalation/intercalation, and serious capacity loss. Herein, Mg-Ni co-substituted K1/2Mn5/6Mg1/12Ni1/12O2 is designed as a promising cathode material for PIBs, with suppressed phase transitions that occurred in K1/2MnO2 and improved K+ storage performance. Part of Mg2+ and Ni2+ occupies the K+ layer, playing the role of a "nailed pillar", which restrains metal oxide layer gliding during the K+ (de)intercalation. The "Mg-Ni pinning effect" not only suppresses the phase transitions but also reduces the cell volume variation, leading to the improved cycle performance. Moreover, K1/2Mn5/6Mg1/12Ni1/12O2 has low activation barrier energy for K+ diffusion and high electron conductivity as demonstrated by first-principles calculations, resulting in better rate capability. In addition, K1/2Mn5/6Mg1/12Ni1/12O2 also delivers a higher reversible capacity owing to the participation of the Ni element in electrochemical reactions and the pseudocapacitive contribution. This study provides a basic understanding of structural evolution in layered Mn-based oxides and broadens the strategic design of cathode materials for PIBs.