Structural Phase Transition Research Articles

Acoustic Shock Wave-Induced Rutile to Anatase Phase Transition of TiO2 Nanoparticles and Exploration of Their Unconventional Thermodynamic Structural Transition Path of Crystallization Behaviors.

Titanium dioxide (TiO2) is one of the most well-known and long-standing polymorphic materials in the transition metal oxide group of materials. The transition from rutile to anatase is one of the long-standing fundamental questions among materials science researchers because seeking the nucleation site at the beginning of the phase transition is highly challenging. Until now, there have been no studies on the unconventional structural phase transition of TiO2 nanoparticles by acoustic shock waves. In the present study, this work provides the first evidence on the solid-state nanostructure of the rutile-to-anatase phase transition of TiO2 by acoustic shock waves whereby these phase transition results are evaluated by Raman spectroscopy, thermal calorimetry, X-ray photoelectron spectroscopy, and microscopic techniques. We propose a novel mechanism for the occurrence of the rutile-to-anatase phase transition based on thermophysical properties and shock wave-induced melting concepts. Under shocked conditions, the R-A phase transition occurs because of the anatase phase's lower interfacial energy (γL/A) and surface energy compared to rutile. We strongly believe that the present work can provide in-depth insight into understanding the crystallization concepts of the TiO2 NPs under extreme conditions, especially with regard to the rutile-to-anatase phase transition.

Boosting the intrinsic kinetics of lithium vanadium phosphate via an electrochemically active cross-link framework

The monoclinic lithium vanadium phosphate Li3V2(PO4)3 (LVP) is considered a promising cathode for lithium-ion batteries (LIBs) due to its high working voltage (>4.0 V, vs. Li+/Li) and high theoretical specific capacity (197 mAh g−1). However, the electrochemical procedure accompanied by three-electron reactions in LVP has proven challenging due to the complexity or asymmetry of the reaction pathways, thus limiting its wide application. Herein, an electrochemically active cross-link framework of LVP, LiFe0.3Mn0.7PO4 (LFMP) and graphene are successfully synthesized by an in situ catalytic process, which enables stable cycling and high-rate capabilities up to 4.8 V (vs. Li+/Li). Graphene-like carbon can be formed in situ with VOx as the catalyst and polyvinyl alcohol as the carbon source, and LFMP also inhibits the growth of LVP particles, allowing rapid Li+ and electron transport in the cathodes. Both in situ and ex situ X-ray diffraction prove that the cross-link framework efficiently smooths the lattice mismatch and achieves highly reversible structural phase transitions. The prepared 0.9LVP·0.1LFMP is able to provide a superior rate capability of 123 mAh g−1 at 20 C. After 150 cycles, the 0.9LVP·0.1LFMP shows 97.4 % capacity retention even under a voltage of 4.8 V (vs. Li+/Li). This work develops a new strategy for the future design of high-voltage and high-power cathode materials for LIBs.

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

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

Air-stable manganese-based layered oxide cathode enabled by surface modification and doping strategy for advanced sodium-ion batteries

P2-type layered oxide materials have attracted widespread attention as advanced cathodes for sodium-ion batteries due to their excellent rate potential and attractive cost-effectiveness. However, the unexpected dissolution of transition metal (TM) ions and the annoying Jahn-Teller effect leading to rapid capacity fading and low capacity remain obstacles to their commercial applications. To tackle these handicaps, we introduced a synergistic effect based on surface modification and doping strategies to obtain air-stable sodium carbonate (Na2CO3) protective aluminum (Al)-doped manganese-based layered oxide cathode. The surface Na2CO3 nanolayer is created by converting residual alkali ions, which enhances the air stability of the cathode and scavenges hydrofluoric acid into the fluoride-rich cathode electrolyte interphase layer during cycling, resulting in a steady interfacial interaction. In addition, Al doping causes TMO6-octahedral shrinkage and inhibits structural distortion, thereby affecting structural evolution and phase transition. These findings provide valuable insights into improving the performance of layer oxide cathodes for next-generation low-cost batteries.

Pressure‐Enhanced Superconductivity and Structural Phase Transition in Layered Sn4P3

High pressure provides a unique tuning method depending on structure modulation to explore the structure–property relationship. Herein, the pressure‐induced structural phase transformation and enhanced superconductivity in a layered binary phosphide Sn4P3 are reported. Comprehensive measurements using in situ synchrotron X‐Ray diffraction and Raman spectroscopy reveal a structural phase transition with mild distortion of SnP3 building blocks and interlayer shrinkage under high pressure. This differs from a conventional trigonal SnAs(P)3 to square SnAs(P)4 topotactic transition in SnAs(P)‐based compound. Through this structure reconstruction under high pressure, electron distribution has been reorganized and phonons have softened, facilitating a high superconducting temperature (Tc) value of 7.8 K at 34.9 GPa, which is almost six times higher than its ambient value. The study introduces a new transition route in layered SnAs/SnP‐based intermetallic materials and provides insight into the structural and electronic changes under high pressure for Sn4P3.

Effect of Sr substitution on the structural, dielectric and ferroelectric property of BaTiO3

We have performed a comprehensive study to explore the effect of Sr substitution on the structural and ferroelectric properties of BaTiO3(BTO) with compositions Ba1-xSrxTiO3for 0 ⩽x⩽ 1. The room temperature structural investigation inferred that the samples with compositionsx> 0.30 has cubic phase instead of tetragonal as for pristine BTO. The temperature dependent dielectric studies illustrate that all well-known three structural phase transitions of BTO are coming closer to each other and the cubic phase is shifted towards lower temperature with increasing Sr content. The frequency dependent dielectric measurements show that there exists the mesoscopic subdomain, whose relaxation time decreases with increasing Sr concentration. The Sr substitution enhanced the ferroelectric properties and maximum remnant polarization at room temperature is observed for 20% Sr substituted sample. The frequency dependent dielectric measurements illustrate the relaxation which could be due to the mesoscopic subdomain, and its relaxation time decreases with increasing Sr concentration. The frequency dependentP-Emeasurements at room temperature infer that for 30% Sr substituted sample, the ferroelectric domain switching is dominated by the rate of nucleation whereas in other compositions forx< 0.3, it is governed by the domain wall speed. The Raman measurements infer the rearrangement of the domain configuration with Sr substitution. Modification in the intensity of the E(TO4) and A(TO3) Raman modes with electric field is also observed for 30% Sr substituted sample and the origin of this is also discussed.

Optical tunning of high-luminescent iodine-substituted CsPb2(Br0.84I0.16)5 under pressure

Metal halide compounds hold significant interest for optoelectronics, given their substantial potential for solar cells and light-emitting applications. Low-dimensional (0D, 1D, and 2D) metal halide perovskites or perovskite-like compounds exhibit various compositions with soft lattices and modular optical properties. Thus, the finding of new strategies to further improve such properties is a current research challenge. In this scenario, the 2D perovskite-like compound CsPb2Br5 has attracted attention due to its structural stability and favorable optical properties. This study presents the pressure-induced structural phase transitions of the iodine substituted CsPb2(Br0.84I0.16)5. This substitution induces strong green photoluminescence in single crystals at ambient conditions. High-pressure optical and synchrotron X-ray diffraction experiments reveal a tetragonal-tetragonal structural phase transitions around 1 GPa, while the photoluminescence emission is quenched around 2.7 GPa. Additionally, a new high-pressure orthorhombic phase is identified in the iodine-doped compound beyond 4.5 GPa. Further analysis of structural features prove that the pressure dependent photoluminescence behavior is directly related to structural distortions observed upon pressure increase.

High pressure ferroelectric-like semi-metallic state in Eu-doped BaTiO3.

We have conducted a detailed high-pressure (HP) investigation on Eu-doped BaTiO3 using angle-resolved x-ray diffraction, Raman spectroscopy, and dielectric permittivity measurements. The x-ray diffraction data analysis shows a pressure-induced structural phase transition from the ambient tetragonal to the mixed cubic and tetragonal phases above 1.4GPa. The tetragonality of the sample due to the internal deformation of the TiO6 octahedra caused by the charge difference from Eu doping cannot be lifted by pressure. Softening, weakening, and disappearance of low-frequency Raman modes indicate ferroelectric tetragonal to the paraelectric cubic phase transition. However, the pressure-induced increase in the intensity of [E(LO), A1(LO)] and the octahedral breathing modes indicate that the local structural inhomogeneity remains in the crystal and is responsible for spontaneous polarization in the sample. The low-frequency electronic scattering response suggests pressure-induced carrier delocalization, leading to a semi-metallic state in the system. Our HP dielectric constant data can be explained by the presence of pressure-induced localized clusters of microscopic ferroelectric ordering. Our results suggest that the HP phase coexistence leads to a ferroelectric-like semi-metallic state in Eu-doped BaTiO3 under extreme quantum limits.

Atomic resolution scanning transmission electron microscopy at liquid helium temperatures for quantum materials

Fundamental quantum phenomena in condensed matter, ranging from correlated electron systems to quantum information processors, manifest their emergent characteristics and behaviors predominantly at low temperatures. This necessitates the use of liquid helium (LHe) cooling for experimental observation. Atomic resolution scanning transmission electron microscopy combined with LHe cooling (cryo-STEM) provides a powerful characterization technique to probe local atomic structural modulations and their coupling with charge, spin and orbital degrees-of-freedom in quantum materials. However, achieving atomic resolution in cryo-STEM is exceptionally challenging, primarily due to sample drifts arising from temperature changes and noises associated with LHe bubbling, turbulent gas flow, etc. In this work, we demonstrate atomic resolution cryo-STEM imaging at LHe temperatures using a commercial side-entry LHe cooling holder. Firstly, we examine STEM imaging performance as a function of He gas flow rate, identifying two primary noise sources: He-gas pulsing and He-gas bubbling. Secondly, we propose two strategies to achieve low noise conditions for atomic resolution STEM imaging: either by temporarily suppressing He gas flow rate using the needle valve or by acquiring images during the natural warming process. Lastly, we show the applications of image acquisition methods and image processing techniques in investigating structural phase transitions in Cr2Ge2Te6, CuIr2S4, and CrCl3. Our findings represent an advance in the field of atomic resolution electron microscopy imaging for quantum materials and devices at LHe temperatures, which can be applied to other commercial side-entry LHe cooling TEM holders.

(C5H9NH3)2CuBr4 : A metal-organic two-ladder quantum magnet

Low-dimensional quantum magnets are a versatile materials platform for studying the emergent many-body physics and collective excitations that can arise even in systems with only short-range interactions. Understanding their low-temperature structure and spin Hamiltonian is key to explaining their magnetic properties, including unconventional quantum phases, phase transitions, and excited states. We study the metal-organic coordination compound (C5H9NH3)2CuBr4 and its deuterated counterpart, which upon its discovery was identified as a candidate two-leg quantum (S=12) spin ladder in the strong-leg coupling regime. By growing large single crystals and probing them with both bulk and microscopic techniques, we deduce that two previously unknown structural phase transitions take place between 136 and 113 K. The low-temperature structure has a monoclinic unit cell that gives rise to two inequivalent spin ladders. We further confirm the absence of long-range magnetic order down to 30 mK and investigate the implications of this two-ladder structure for the magnetic properties of (C5H9NH3)2CuBr4 by analyzing our own specific-heat and susceptibility data. Published by the American Physical Society 2024

Pressure-induced structural, electronic, and superconducting phase transitions in TaSe3

Abstract TaSe3 has garnered significant research interests due to its unique quasi-one-dimensional crystal structure, which gives rise to distinctive properties. Using crystal structure search and first-principles calculations, we systematically investigated the pressure-induced structural and electronic phase transitions of quasi-one-dimensional TaSe3 up to 100 GPa. In addition to the ambient pressure phase (P21/m-I), we identified three high-pressure phases: P21/m-II, Pnma, and Pmma. For the P21/m-I phase, the inclusion of spin–orbit coupling (SOC) results in significant SOC splitting and changes in the band inversion characteristics. Furthermore, band structure calculations for the three high-pressure phases indicate metallic natures, and the electron localization function suggests ionic bonding between Ta and Se atoms. Our electron–phonon coupling calculations reveal a superconducting critical temperature of approximately 6.4 K for the Pmma phase at 100 GPa. This study provides valuable insights into the high-pressure electronic behavior of quasi-one-dimensional TaSe3.

Anatase to rutile transition in TiO2 thin films: Role of tantalum and oxygen

The present study discusses the optimal solubility limit of tantalum in anatase TiO2 thin films (dopant solubility limit) and its effect on crystal structure transformation to the rutile phase. The study also focuses on the role of lattice oxygen in this structural phase transition. The detailed chemical composition, constitution, and phase of these sputter-deposited thin films are correlated with their electrical and optical properties to understand the disparity between total impurity concentration in these films and actual impurity substitution into the host lattice sites (dopant content). Reduced oxygen vacancies from the oxygen lattice sites and/or Ta substitution in Ti lattice sites are found to hinder the anatase to rutile phase transformation in TiO2 thin films. Our experimental data indicates the solubility limit of Ta being < 5 at% in TiO2. Similar behavior is seen when Ta is replaced with Nb in TiO2 thin films. Moreover, an increased oxygen and/or impurity concentration is found to lead to impurity-rich-oxides in these films, degrading the electrical conductivity.

Fundamental influence of irreversible stress–strain properties in solids on the validity of the ramp loading method

The widely used quasi-isentropic ramp loading technique relies heavily on back-calculation methods that convert the measured free-surface velocity profiles to the stress–density states inside the compressed sample. Existing back-calculation methods are based on one-dimensional isentropic hydrodynamic equations, which assume a well-defined functional relationship P(ρ) between the longitudinal stress and density throughout the entire flow field. However, this kind of idealized stress–density relation does not hold in general, because of the complexities introduced by structural phase transitions and/or elastic–plastic response. How and to what extent these standard back-calculation methods may be affected by such inherent complexities is still an unsettled question. Here, we present a close examination using large-scale molecular dynamics (MD) simulations that include the detailed physics of the irreversibly compressed solid samples. We back-calculate the stress–density relation from the MD-simulated rear surface velocity profiles and compare it directly against the stress–density trajectories measured from the MD simulation itself. Deviations exist in the cases studied here, and these turn out to be related to the irreversibility between compression and release. Rarefaction and compression waves are observed to propagate with different sound velocities in some parts of the flow field, violating the basic assumption of isentropic hydrodynamic models and thus leading to systematic back-calculation errors. In particular, the step-like feature of the P(ρ) curve corresponding to phase transition may be completely missed owing to these errors. This kind of mismatch between inherent properties of matter and the basic assumptions of isentropic hydrodynamics has a fundamental influence on how the ramp loading method can be applied.

Superconductivity under pressure in a chromium-based kagome metal.

Superconductivity in a highly correlated kagome system has been theoretically proposed for years (refs. 1-5), yet the experimental realization is hard to achieve6,7. The recently discovered vanadium-based kagome materials8, which exhibit both superconductivity9-11 and charge-density-wave orders12-14, are nonmagnetic8,9 and weakly correlated15,16. Thus these materials are unlikely to host the exotic superconductivity theoretically proposed. Here we report the discovery of a chromium-based kagome metal, CsCr3Sb5, which is contrastingly featured with strong electron correlations, frustrated magnetism and characteristic flat bands close to the Fermi level. Under ambient pressure, this kagome metal undergoes a concurrent structural and magnetic phase transition at 55 K, with a stripe-like 4a0 structural modulation. At high pressure, the phase transition evolves into two transitions, possibly associated with charge-density-wave and antiferromagnetic spin-density-wave orderings. These density-wave-like orders are gradually suppressed with pressure and, remarkably, a superconducting dome emerges at 3.65-8.0 GPa. The maximum of the superconducting transition temperature, Tcmax = 6.4 K, appears when the density-wave-like orders are completely suppressed at 4.2 GPa, and the normal state exhibits a non-Fermi-liquid behaviour, reminiscent of unconventional superconductivity and quantum criticality in iron-based superconductors17,18. Our work offers an unprecedented platform for investigating superconductivity in correlated kagome systems.

Unexpected Observation of Disorder and Multiple Phase-Transition Pathways in Shock-Compressed Zr.

The response of materials under dynamic compression involves a complex interplay of various deformation mechanisms aimed at relieving shear stresses, yielding a remarkable diversity in material behavior. In this Letter, we utilize femtosecond x-ray diffraction coupled with nanosecond laser compression to reveal an intricate competition between multiple shear-relieving mechanisms within an elemental metal. Our observations in shocked-compressed single-crystal Zr indicate a disorder-mediated shear relaxation at lower pressures. Above the phase-transition pressure, we observe the increasing contribution of structural phase transition in relieving shear stress. We detect not one but three concurrent pathways during the transition from the hcp to a hex-3 structure. These complex dynamics are partially corroborated through multimillion-atom molecular dynamics simulations employing a machine-learned interatomic potential. Our observation of multiple concurrent pathways and disorder during shock compression underscore the far greater intricacies in the dynamic response of metals than previously assumed.

Suppression of a Structural Phase Transition by an Orientational Disorder of Counteranions in an Organic Conductor, β″-β″-(BEDT-TTF)2ClC2H4SO3.

In 2022, we reported that the β″-(BEDT-TTF)2ClC2H4SO3 salt (1) has a phase transition at 210 K on cooling and 260 K on heating, which was suggested as a nondoped-to-doped transition. During the synthesis of 1, a second salt was coproduced, the structure and properties of which are reported here. The new salt β″-β″-(BEDT-TTF)2ClC2H4SO3 (2) has the same composition and is isomorphous to 1L, the low-temperature phase of 1. However, the salt shows no phase transition. 1H, the high-temperature phase of 1, displays rotational disorders of the -SO3- groups. In contrast, the anions in 2 have no rotational disorders but have orientational disorders. Approximately 13% of the anions in 2 have their orientation as opposed to the remaining anions. The geometrically calculated shortest O···O distance is 2.24 Å if neighbor -SO3- groups are able to rotate freely. This is 1.1 Å shorter than the sum of the van der Waals radii, and therefore, this is too close to allow free rotation. Therefore, it is proposed that 2 has no rotational disorder, which leads to no phase transition as is observed in 1.

Corrections of Electron–Phonon Coupling for Second‐Order Structural Phase Transitions

Structural phase transitions are accompanied by a movement of one nucleus (or a few) in the crystallographic unit cell. If the nucleus movement is continuous, a second‐order phase transition without latent heat results, whereas an abrupt nucleus displacement indicates a first‐order phase transition with accompanying latent heat. Herein, a Hamiltonian including electron–phonon coupling (EPC) as proposed by Kristoffel and Konsel is taken. Contrary to their treatment, both the kinetic energy of the nucleus and its position are treated. The interaction of the many‐electron system with the single nucleus is taken into account by the Born–Oppenheimer approximation and perturbative expressions for the free energies are derived. The nuclei corrections due to the entangled electrons are found to be minor, but highlight the importance of the symmetry breaking at low temperature. Furthermore the free energy for a canonical ensemble is computed, whereas Kristoffel and Konsel use a grand canonical ensemble, which allows to derive more stringent bounds on the free energy. For the zero‐order nucleus correction, the shift of the phase transition temperature by evaluating the free energy is deduced.

Structural Phase Transition and Disproportionation of MnF3 Under High Pressure and High Temperature.

Materials that once suffered under high-pressure and high-temperature conditions often display unusual phenomena that challenge traditional understanding. MnF3, an intermediate valence state Mn-F compound, exhibits a distorted octahedral crystal structure influenced by the Jahn-Teller effect. Here we report the structural phase transition and self-disproportionation of MnF3 under high pressure and high temperature. The initial octahedra phase I2/a-MnF3 transforms into the hendecahedra Pnma phase under high pressure. Subsequently, we found that molten Pnma-MnF3 self-disproportionate into MnF2 and MnF4 with the aid of laser heating at a pressure above 57.1 GPa. Raman spectra and UV-vis absorption experiments confirmed these changes that were ultimately confirmed by synchrotron radiation XRD. The equation of states for the volume with the pressure of these Mn-F compounds was also given. This work expands the study of Mn-F systems and provides guidance for the behavior of transition metal fluorides under high pressures and high temperatures.

Lattice Softening and Band Convergence in GeTe-Based Alloys for High Thermoelectric Performance.

GeTe-based alloys have been studied as promising TE materials in the midtemperature range as a lead-free alternate to PbTe due to their nontoxicity. Our previous study on GeTe1-xIx revealed that I-doping increases lattice anharmonicity and decreases the structural phase transition temperature, consequently enhancing the thermoelectric performance. Our current work elucidates the synergistic interplay between band convergence and lattice softening, resulting in an enhanced thermoelectric performance for Ge1-ySbyTe0.9I0.1 (y = 0.10, 0.12, 0.14, and 0.16). Sb doping in GeTe0.9I0.1 serves a double role: first, it leads to lattice softening, thereby reducing lattice thermal conductivity; second, it promotes a band convergence, thus a higher valley degeneracy. The presence of lattice softening is corroborated by an increase in the internal strain ratio observed in X-ray diffraction patterns. Doping also introduces phonon scattering centers, further diminishing lattice thermal conductivity. Additionally, variations in the electronic band structure are indicated by an increase in density of state effective mass and a decrease in carrier mobility with Sb concentration. Besides, Sb doping optimizes the carrier concentration efficiently. Through a two-band modeling and electronic band structure calculations, the valence band convergence due to Sb doping can be confirmed. Specifically, the energy difference between valence bands progressively narrows upon Sb doping in Ge1-ySbyTe0.9I0.1 (y = 0, 0.02, 0.05, 0.10, 0.12, 0.14, and 0.16). As a culmination of these effects, we have achieved a significant enhancement in zT for Ge1-ySbyTe0.9I0.1 (y = 0.10, 0.12, 0.14, and 0.16) across the entire range of measured temperatures. Notably, the sample with y = 0.12 exhibits the highest zT value of 1.70 at 723 K.

The structural mechanisms of pressure-induced phase transitions in the Carpy-Galy phase layered perovskites

In layered perovskites with the Carpy-Galy structural type, similar structural phase transitions occur under high pressure. These structural changes, which are crucial for the pressure-induced phase transition in layered perovskite, were analyzed based on experimental X-ray diffraction data. The tilting of the Ti-O6 octahedra and the distortion of the arrangement of rare-earth atoms were studied in detail. Changes in these structural features in layered perovskite serve as common indicators of the phase transition to the monoclinic phase that occurs under high pressure application.