Order-disorder Phase Transition Research Articles

SHINERS Study of Chloride Order-Disorder Phase Transition and Solvation of Cu(100).

Shell-isolated nanoparticle enhanced Raman spectroscopy (SHINERS) and density functional theory (DFT) are used to probe Cl- adsorption and the order-disorder phase transition associated with the c(2 × 2) Cl- adlayer on Cu(100) in acid media. A two-component ν(Cu-Cl) vibrational band centered near 260 ± 1 cm-1 is used to track the potential dependence of Cl- adsorption. The potential dependence of the dominant 260 cm-1 component tracks the coverage of the fluctional c(2 × 2) Cl- phase on terraces in good agreement with the normalized intensity of the c(2 × 2) superstructure rods in prior surface X-ray diffraction (SXRD) studies. As the c(2 × 2) Cl- coverage approaches saturation, a second ν(Cu-Cl) component mode emerges between 290 and 300 cm-1 that coincides with the onset and stiffening of step faceting where Cl- occupies the threefold hollow sites to stabilize the metal kink saturated Cu <100> step edge. The formation of the c(2 × 2) Cl- adlayer is accompanied by the strengthening of ν(O-H) stretching modes in the adjacent non-hydrogen-bonded water at 3600 cm-1 and an increase in hydronium concentration evident in the flanking H2O modes at 3100 cm-1. The polarization of the water molecules and enrichment of hydronium arise from the combination of Cl- anionic character and lateral templating provided by the c(2 × 2) adlayer, consistent with SXRD studies. At negative potentials, Cl- desorption occurs followed by development of a sulfate νs(S═O) band. Below -1.1 V vs Hg/HgSO4, a new 200 cm-1 mode emerges congruent with hydride formation and surface reconstruction reported in electrochemical scanning tunneling microscopy studies.

Unraveling the atomic mechanism of the disorder–order phase transition from γ-Ga2O3 to β-Ga2O3

In this paper, we employ in situ transmission electron microscopy to study the disorder–order phase transition from amorphous Ga2O3 to γ-Ga2O3 and then to β-Ga2O3. The in situ studies are complemented by ex situ annealing experiments, of which the results are analyzed by x-ray diffraction and high resolution (scanning) transmission electron microscopy. Amorphous Ga2O3 deposited at 100 °C by molecular beam epitaxy crystallizes at 470 °C in the γ phase (Fd3̄m), which undergoes a phase transition to the β phase above 500 °C. Between 500° and 900 °C, we find a mixture of γ-Ga2O3 and β-Ga2O3 coexisting. Above 950 °C, we find only β-Ga2O3. Through our analyses and by considering symmetry relations, we have constructed a coincidence site lattice of both structures containing a common fcc-type sublattice occupied by oxygen atoms, the cation sites of β-Ga2O3 common to both phases, and partially occupied cation sites in the γ phase corresponding to the interstitial sites in the β phase. We assign the atomic displacements within this lattice responsible for transforming the initially disordered spinel structure with partially occupied cation sites into the well-ordered lattice of β-Ga2O3. We identify this transition as a reconstructive disorder-to-order phase transition, mediated by the exchange of cations to next nearest neighbor sites. Our model not only explains recent observations of the formation of γ-Ga2O3 during implantation for n-type doping and the subsequent recovery of β-Ga2O3 following annealing but also holds potential for inspiring understanding in other materials with similar phase transitions.

Organic ferroelastic enantiomers with high Tc and large dielectric switching ratio triggered by order-disorder and displacive phase transition

Molecular-based ferroelastics with dielectric switching properties are highly desirable for their applications on microelectronic dielectric switches, sensors, data storage, and so on. However, the current reports mostly focus on organic-inorganic hybrids containing toxic heavy metal atoms, and the relatively low phase transition temperature limits their application. In this paper, low-toxic organic salt ferroelastic enantiomers (R/S)-4-fluoro-1-azabicyclo[3.2.1]octonium chloride [(R/S)-F-321] were designed and synthesized under the introducing chirality strategy. They undergo a 432F422-type ferroelastic phase transition with a high Curie temperature (Tc) of 470 K, simultaneously exhibiting excellent dielectric switching characteristics. In addition to the ordered-disordered movement of cations, the significant displacement of anions is also responsible for such high Tc and large dielectric switching ratios, which is very rare in molecular-based switching materials. This work enriches the development of molecular ferroelastic switching materials and gives inspiration for the exploration of environmentally friendly high Tc organic salt ferroelastics with prominent switching performances.

In Ukrainian

The review material reveals the question of the influence of impurities on the physical properties of alloys, as well as the influence of gases on processes in alloys. It has been established that the presence of hydrogen affects diffusion in alloys, and gases have a significant effect on the thermoelectromotive force of metals. The paper describes the addition of a third element to binary systems, which can expand or narrow the domain of existence of an ordered phase. The above examples of adding an impurity of vanadium or molybdenum to an alloy of iron and chromium increase the ordering temperature. It has been established that gases can have a significant effect on the thermoelectromotive force of metals and increase the hardness and reduce the ductility of metals, as well as cause their brittleness and delamination. It has been established that hydrogen (H2) in alloys (for example, Fe-Ni and Au-Cu) affects diffusion and atomic ordering processes. Also, a small concentration of hydrogen, as an impurity, can change the electrical resistance of alloys (for example, in a Pd-Au alloy). It has been established that the addition of a third element to binary systems can change the state diagram, which must be taken into account when solving problems for the production of heat treatment modes for alloys, determining the conditions for phase equilibrium, etc. The paper considers the dependence of hydrogen solubility on temperature in metals (Cu, Fe and Al) and establishes the dependence of hydrogen solubility in a metal on the concentration of impurity metals. The temperature dependence of hydrogen solubility in Fe-V alloys is also shown. The shift of the density of state is studied for different distributions of impurity atoms in the alloy in the order-disorder system, and the dependence of the density of states of disordered and ordered solid solutions is studied. The dependence of the relative solubility of atoms introduced into the pores of alloys with an fcc structure (of the Cu3Au type) is indicated, taking into account the solubility, on the parameter χ, which is proportional to the degree of long-range order in the octahedral and tetrahedral pores of the alloys. The dependence of the relative solubility of intercalated atoms in octahedral pores of alloys with a bcc structure (such as CuZn and Fe3Al) is considered. A plot of the dependence of the concentration of dissolved impurity atoms on the degree of order is shown for substitutional alloys with a bcc lattice, where the M2 coefficient is introduced, which does not depend on the degree of order. The effect of pressure as a measure of long-range order is also studied, where its step decreases or increases, or decreases and then increases and vice versa (order-disorder phase transition). An equally important result is the graphic dependence of solubility (c) on pressure (P) in disordered and ordered alloys.

Order-disorder phase transitions significantly improving the upconversion luminescence intensity of BiTa7O19:Er3+/Yb3+

BiTa7O19 (BTO) has two lattice structure, P–6C2 (188) ordered phase and P63/mcm (193) disordered phase. Ordered and disordered BTO:Er3+/Yb3+ upconversion phosphors (UCPs) were obtained by solid sintering with different temperatures. The lattice structure of all the samples was investigated by XRD, SEM and Raman spectroscopy, and upconversion luminescence (UCL) spectra were tested by spectrometers. The green integral UCL intensity of the disordered BTO:Er3+/Yb3+ UCP is 60.76 times than that of the ordered sample. By comparing Er3+/Yb3+ co-doped and Er3+ single-doped UCPs with different structures, it is found that the disordered structure enhances the energy transfer from Yb3+ to Er3+, which may be caused by the disordered structure reducing the distance between Yb3+ and Er3+. The absolute temperature sensitivity of the sample with the highest UCL intensity is 0.01005 K-1 at 352 K. All results suggest that the disordered structure of BTO host can greatly improve green UCL intensity and the disordered BTO:Er3+/Yb3+ UCPs are suitable for the application of optical temperature measurement.

(Battery Division Research Award) Advanced Characterization of Electrochemical Interfaces and Systems for Next-Generation Batteries

Lithium (Li) metal has been considered as an ideal anode for high-energy rechargeable Li batteries while Li nucleation and growth at the nano scale remains mysterious as to achieving reversible stripping and deposition. A few decades of research have been dedicated to this topic and we have seen breakthroughs in novel electrolytes in the last few years, where the efficiency of lithium deposition is exceeding 99.6%. Here, cryogenic-transmission electron microscopy (Cryo-TEM/Cryo-FIB) was used to reveal the evolving nanostructure of Li deposits at various transient states in the nucleation and growth process, in which a disorder-order phase transition was observed as a function of current density and deposition time. More importantly, the complementary techniques such as titration gas chromatography (TGC) reveals the important insights about the phase fraction of solid electrolyte interphases (SEI) and electrochemical deposited Li (EDLi). While cryo-EM has made significant contributions to enabling lithium metal anodes for batteries, its applications in the area of electrochemical interphases such as those in all solid state batteries, beyond lithium batteries are still in the infancy, therefore, I will discuss a few new perspectives about how future advanced imaging and spectroscopic techniques can help to accelerate the innovation of novel energy storage materials and architectures.

On the atomic ordering in the B-sublattice of high-entropy perovskites

Atomic ordering in perovskites has been the subject of intensive research for decades. With the growing interest in high-entropy perovskites (HEP), the issue of atomic ordering is now reaching a new level of significance. Many multi-cationic perovskites have already been synthesized, and some of them exhibit atomic ordering. Therefore, the problems of estimating the phase transition temperature of atomic ordering, determining the type of emerging atomic order, and the distribution of cations in ordered sublattices need to be addressed. In this work, based on the unstrained elastic cation-anion bonds model, we develop a Monte Carlo calculation scheme of atomic order-disorder phase transitions in the B-sublattice of perovskites with arbitrary composition and apply it to the case of HEP. We find that HEP’s may experience rock-salt type atomic ordering, while preserving considerable configurational entropy and essentially becoming ordered disordered perovskites. For many HEP’s, whose synthesis has been already reported in literature or which await their synthesis, we estimate the phase transition temperature Tod, reduced cubic lattice parameters, and the composition of the ordered sublattices. Finally, we derive a simple relation for the estimation of Tod from normalized standard deviation of the unstrained cation-anion bond lengths of atoms in the B-sublattice, which can be easily calculated.

Collective behavior of self-propelled particles with heading estimation via focal observation

Animals, including humans, often achieve velocity alignment by observing their neighbors from their own perspective rather than form a bird’s-eye view. In this study, we explore a particular implementation of this idea, where particles estimate the heading of their neighbors based on their own focal view observations, thereby achieving velocity alignment. Two types of observations are used to estimate the heading of neighbors in this study: the relative position of neighbors at two adjacent moments, and the movement of the focal particle itself. Simulation results show that noise amplitude η arising during observations and the weight parameter s denoting the ratio of noise contained in the two types of observations can induce continuous order–disorder phase transition. The probability density distribution of the noise contained in different models is statistically analyzed, and results show that the type of phase transition mainly depends on the variance of the noise. Furthermore, an optimal value of s is found in our model that makes the model tolerate large noise amplitude. Our findings suggest that the focal view observation plays an important role in collective motion.

Phase Transitions, Dielectric Response, and Nonlinear Optical Properties of Aziridinium Lead Halide Perovskites.

Hybrid organic-inorganic lead halide perovskites are promising candidates for next-generation solar cells, light-emitting diodes, photodetectors, and lasers. The structural, dynamic, and phase-transition properties play a key role in the performance of these materials. In this work, we use a multitechnique experimental (thermal, X-ray diffraction, Raman scattering, dielectric, nonlinear optical) and theoretical (machine-learning force field) approach to map the phase diagrams and obtain information on molecular dynamics and mechanism of the structural phase transitions in novel 3D AZRPbX3 perovskites (AZR = aziridinium; X = Cl, Br, I). Our work reveals that all perovskites undergo order-disorder phase transitions at low temperatures, which significantly affect the structural, dielectric, phonon, and nonlinear optical properties of these compounds. The desirable cubic phases of AZRPbX3 remain stable at lower temperatures (132, 145, and 162 K for I, Br, and Cl) compared to the methylammonium and formamidinium analogues. Similar to other 3D-connected hybrid perovskites, the dielectric response reveals a rather high dielectric permittivity, an important feature for defect tolerance. We further show that AZRPbBr3 and AZRPbI3 exhibit strong nonlinear optical absorption. The high two-photon brightness of AZRPbI3 emission stands out among lead perovskites emitting in the near-infrared region.

Dynamics, statistics, and task allocation of foraging ants.

Ant foraging is one of the most fascinating examples of cooperative behavior observed in nature. It is well studied from an entomology viewpoint, but there is currently a lack of mathematical synthesis of this phenomenon. We address this by constructing an ant foraging model that incorporates simple behavioral rules within three task groups of the ant colony during foraging (foragers, transporters, and followers), pheromone trails, and memory effects. The motion of an ant is modeled as a discrete correlated random walk, with a characteristic zigzag path that is congruent with experimental data. We simulate the foraging cycle, which consists of ants searching for food, transporting food, and depositing chemical trails to recruit and orient more ants (en masse) to the food source. This allows us to gain insights into the basic mechanism of the cooperative interactions between ants and the dynamical division of labor within an ant colony during foraging to achieve optimal efficiency. We observe a disorder-order phase transition from the start to the end of a foraging process, signaling collective motion at the population level. Finally, we present a set of time delay ODEs that corroborates with numerical simulations.

Pressure-Modulated Anomalous Organic-Inorganic Interactions Enhance Structural Distortion and Second-Harmonic Generation in MHyPbBr3 Perovskite.

Organic-inorganic halide perovskites possess unique electronic configurations and high structural tunability, rendering them promising for photovoltaic and optoelectronic applications. Despite significant progress in optimizing the structural characteristics of the organic cations and inorganic framework, the role of organic-inorganic interactions in determining the structural and optical properties has long been underappreciated and remains unclear. Here, by employing pressure tuning, we realize continuous regulation of organic-inorganic interactions in a lead halide perovskite, MHyPbBr3 (MHy+ = methylhydrazinium, CH3NH2NH2+). Compression enhances the organic-inorganic interactions by strengthening the Pb-N coordinate bonding and N-H···Br hydrogen bonding, which results in a higher structural distortion in the inorganic framework. Consequently, the second-harmonic-generation (SHG) intensity experiences an 18-fold increase at 1.5 GPa, and the order-disorder phase transition temperature of MHyPbBr3 increases from 408 K under ambient pressure to 454 K at the industrially achievable level of 0.5 GPa. Further compression triggers a sudden non-centrosymmetric to centrosymmetric phase transition, accompanied by an anomalous bandgap increase by 0.44 eV, which stands as the largest boost in all known halide perovskites. Our findings shed light on the intricate correlations among organic-inorganic interactions, octahedral distortion, and SHG properties and, more broadly, provide valuable insights into structural design and property optimization through cation engineering of halide perovskites.

A tensor renormalization group analysis of the Blume–Capel model inspired by game theory

After showing that it can be parametrized as the elementary coordination game of evolutionary game theory, this paper analyzes the Blume–Capel model using the tensor renormalization group method introduced by Michael Levin and Cody P. Nave. The results obtained along the cross sections defined by the coordination game parametrization expand and corroborate earlier findings regarding the location, order, and critical properties of the order–disorder phase transitions in both the zero-field and non-zero-field versions of the Blume–Capel model.

Shock wave induced order to disorder type phase transition of cobalt chloride hexahydrate doped l-histidine hydrochloride monohydrate single crystal

The impact of supersonic shock waves upon materials is one of the fascinating areas of active research in material science. Phase transition behaviour of materials, when subjected to shock waves, is also of great interest in this field. In the present investigation, we have proved the impact of shock wave-induced order–disorder type phase transition of cobalt chloride hexahydrate doped L-histidine hydrochloride monohydrate single crystal. The test crystal was subjected to the corresponding shock pulse counts of 0, 1, 2, 3, and 4 with Mach number 1.7 until the third shock condition, there wasn't a phase change; however, in the fourth shocked condition, there was a phase transition of the order–disorder type noted. X-ray diffractometry, Raman spectroscopy, and UV–Visible spectroscopy are three different analytical techniques that have been used to confirm the aforementioned phase transitions. The order–disorder phase transition enables the investigation of novel aspects of a material's structural properties. The grown crystal had reacted to shock wave exposure in terms of the type of phase transition order–disorder.

Order–disorder phase transition and elastic-to-plastic vortex creep crossover in a triclinic iron pnictide superconductor (Ca_{0.85}La_{0.15})_{10}(Pt_3As_8)(Fe_2As_2)_5

Vortex matter in layered high-T_c superconductors, including iron-pnictides, undergo several thermodynamic phase transitions due to the complex interplay of pinning energy, thermal energy and elastic energy. Moreover, the presence of anisotropy makes their vortex physics even more intriguing. Here, we report a detailed vortex dynamics study, using dc magnetization measurements, in a triclinic iron-pnictide superconductor (Ca_{0.85}La_{0.15})_{10}(Pt_3As_8)(Fe_2As_2)_5, with a superconducting transition temperature, T_csim 31 K. A second magnetization peak (SMP) feature is observed for magnetic field perpendicular (Hparallelc) and parallel (Hparallelab) to the crystal plane. However, its fundamental origin is quite different in both directions. For Hparallelc, the SMP can be well explained using an elastic-to-plastic vortex creep crossover, using collective creep theory. In addition, a possible rhombic-to-square vortex lattice phase transition is also observed for fields in between the onset-field and peak-field related to the SMP. On the other hand, for Hparallelab, a clear signature of an order-disorder vortex phase transition is observed in the isothermal M(H) measurements at Tge 6 K. The disordered phase exhibits the characteristics of entangled pinned vortex-liquid. We construct a comprehensive vortex phase diagram by displaying characteristic temperatures and magnetic fields for both crystal geometries in this unique superconducting compound. Our study sheds light on the intricate vortex dynamics and pinning in an iron-pnictide superconductor with triclinic symmetry.

Synchronous Switching of Dielectric Constant and Photoluminescence in Cyanidonitridorhenate-Based Crystals.

Switching of multiple physical properties by external stimuli in dynamic materials enables applications in, e.g., smart sensors, biomedical tools, as well as data-storage devices. Among stimuli-responsive materials, inorganic-organic molecular hybrids exhibiting thermal order-disorder phase transitions were tested as promising molecular switches of electrical characteristics, including dielectric constant. We aimed at broadening the multifunctional potential of such hybrid materials towards the switching of not only electrical but also other physical properties, e.g., light emission. We report two ionic salts based on luminescent tetracyanidonitridorhenate(V) anions bearing two different diamine ligands, 1,2-diaminoethane (1) and 1,3-diaminopropane (2), both crystallizing with polar N-methyl-dabconium cations. They exhibit an order-disorder phase transition related to the heating-induced turning-on of the rotation of polar cations. This leads to a unique synchronous switching of the dielectric constant as well as metal-complex-centered photoluminescence, as demonstrated by changes in, e.g., emission lifetime. The roles of organic cations, non-trivial Re(V) complexes, and their interaction in achieving the coupled thermal switching of electrical and optical properties are discussed utilizing experimental and theoretical approaches.

Order-Disorder Phase Transition and Ionic Conductivity in a Li2B12H12 Solid Electrolyte.

Temperature-induced phase transitions and ionic conductivities of Li2B12H12 and LiCB11H12 were simulated with the use of machine learning interatomic potentials based on van der Waals-corrected density functional theory (rev-vdW-DF2 functional). The simulated temperature of order-disorder phase transition, lattice parameters, diffusion, ionic conductivity, and activation energies are in good agreement with experimental data. Our simulations of Li2B12H12 uncover the importance of the reorientational motion of the [B12H12]2- anion. In the ordered α-phase (T < 625 K), these anions have well-defined orientations, while in the disordered β-phase (T > 625 K), their orientations are random. In vacancy-rich systems, its complete rotation was observed, while in the ideal crystal, the anions display limited vabrational motion, indicating the static nature of the phase transition without dynamic disordering. The use of machine learning interatomic potentials has allowed us to study large systems (>2000 atoms) in long (nanosecond-scale) molecular dynamics runs with ab initio quality.

Order–disorder phase transition between high- and low-Z′ crystal structures: crystallographic and non-linear optics study on transition

Order–disorder phase transition between high- and low-Z′ crystal structures: crystallographic and non-linear optics study on transition

Critical behavior of the fluctuation heat capacity near the glass transition of metallic glasses

The high-frequency shear modulus of five Zr-, Pd-, Cu-based conventional and two high-entropy bulk metallic glasses was measured in a wide temperature range up to the beginning of crystallization. Using these data and general thermodynamic relations, the “fluctuation” heat capacity ΔCf determined by local structural fluctuations in the defect regions is introduced and calculated. It is found that ΔCf temperature dependence for all metallic glasses has a large peak located slightly below or above the glass transition temperature but clearly lower than the crystallization onset temperature. The form of this peak resembles the characteristic λ-peak typical for order–disorder phase transitions. It is suggested that this ΔCf-peak reflects certain underlying critical phenomenon. The critical temperature T0 (peak temperature) and corresponding critical index α are determined. Averaged over all seven metallic glasses under investigation in the initial and relaxed states, the critical index <α>=0.26. The results obtained indicate that the fluctuations of thermal energy near the glass transition bear the marks of a continuous phase transition. However, the derived critical index is between those corresponding to a second-order phase transition (α≈0.1) and a critical transition characterized by a tricritical point (α≈0.5).

Ordered L10-FeNi (111) epitaxial thin film on Al2O3 (0001) substrate: Molecular beam epitaxy growth and characterizations

Ordered hard magnetic L10-FeNi has attracted attention as a candidate for rare-earth-free permanent magnet with a large maximum magnetic energy product. Fabricating L10-FeNi is a big challenge using conventional methods due to its low order-disorder transition temperature, 320 °C. In this work, high-quality ordered L10-FeNi films were fabricated by using molecular beam epitaxy directly on Al2O3 (0001) substrate with a two-step co-deposition method below 250 °C. The films were epitaxially grown with [111] orientation, confirmed by reflection high energy electron diffraction and x-ray diffraction patterns. An order-disorder phase transition at 320 °C was observed in temperature dependent electrical resistivity curve. The two-step molecular beam epitaxy grown film exhibited high uniaxial magnetic anisotropy constant, Ku, up to 1.15 × 106 J/m3. The obtained Ku value is comparable to previous result for FeNi along [100] growth direction, indicating an isotropic Ku. This work provides an effective molecular beam epitaxy growth method of high-quality ordered L10-FeNi (111) film for the development of the next-generation rare-earth-free permanent magnet.

Magnetic Properties of CuCr1−xLaxS2 Thermoelectric Materials

The magnetic properties (magnetic susceptibility, magnetic moment) and Weiss constant for lanthanum-doped CuCr1−xLaxS2 (x = 0; 0.005; 0.01; 0.015; 0.03) solid solutions were studied using static magnetochemistry at 80–750 K. The samples were characterized by both powder X-ray diffraction and energy-dispersive X-ray spectroscopy. It was shown that synthesized samples are single-phased up to x ≤ 0.01. The presence of the additional phase in the solid solutions with x &gt; 0.015 caused deviation from the simple isovalent Cr3+→Ln3+ cationic substitution principle. It was found that magnetic susceptibility and the Weiss constant are significantly affected by both magnetic properties and lanthanum concentration for the solid solutions doped up to x = 0.01. The largest magnetic moment value of 3.88 µB was measured for the initial CuCrS2-matrix. The lowest value of 3.77 µB was measured for the CuCr0.99La0.01S2 solid solution. The lowest Weiss constant value of −147 K was observed for the initial matrix; the highest one was observed for CuCr0.99La0.01S2 (−139 K). The largest Seebeck coefficient value of 373 µV/K was measured for CuCr0.985La0.015S2 at 500 K; the obtained value was 3.3 times greater compared to the initial CuCrS2-matrix. The field dependence of the magnetic susceptibility allowed one to conclude the absence of ferromagnetic contributions in the total magnetic susceptibility of CuCr1−xLaxS2. The data on magnetic properties can be successfully utilized to investigate the limits of doping atom suitability and order–disorder phase transition temperature in CuCrS2-based solid solutions.