High-Pressure Phase Transitions of PbTe Using the First-Principles Calculations

High-pressure structural phase transitions in PbTe are investigated by means of the first principles total energy calculations within the generalized gradient approximation （GOAl and local density approximation CLDA） by using the density functional theory. First principle calculation shows that PbTe is stable with the NaCl-type （B1） structure under amSient conditions and transforms to the CsCl-type （B2） structure under high pressure via an intermediate phase. Two candidate structures of the intermediate phase, namely Prima and Cmcm, are chosen for total energy calculations and discussed. It indicates that the intermediate phase adopts the Pnma structure rather than the Cmcm structure, and lattice parameters of the Pnma phase calculated by using OGA and LDA are in consistent with experimental results.

Identification of the pressure-induced phase transition of ZnSe with the positron annihilation method

This paper studies the pressure-induced phase transition between zincblende （B3） and NaC1 （B1） structure ZnSe by using the hydrostatic pressure first-principles pseudopotential plane wave method. The energy-volume and enthalpy- pressure curves are employed to estimate the transition pressure. It is found that ZnSe undergoes a first-order phase transition from the B3 structure to the B1 structure at approximately 15 GPa derived from the energy-volume relation and 14 GPa based on deduction from enthalpy pressure data. The pressure-related positron bulk lifetimes of the two ZnSe structures are calculated with the atomic superposition approximation method. In comparison with the 13.4% reduction in volume of ZnSe at the transition pressure, the positron bulk lifetime decreases more significantly and the relative value declines up to 22.3%. The results show that positron annihilation is an effective technique to identify and characterize the first-order phase transition and can give valuable information about changes in micro-scale, such as volume shrinkage and compressibility.

Unraveling transition-metal-mediated stability of spinel oxide via in situ neutron scattering

The energy materials performance is intrinsically determined by structures from the average lattice structure to the atom arrangement, valence, and distribution of the containing transition metal(TM) elements. Understanding the mechanism of the structure transition and atom rearrangement via synthesis or processing is key to expediting the exploration of excellent energy materials. In this work, in situ neutron scattering is employed to reveal the real-time structure evolution, including the TM-O bonds, lattice,TM valence and the migration of the high-voltage spinel cathode LiNi_(0.5)Mn_(1.5)O_(4). The transition-metalmediated spinel destabilization under the annealing at the oxygen-deficient atmosphere is pinpointed.The formation of Mn^(3+) is correlated to the TM migration activation, TM disordered rearrangement in the spinel, and the transition to a layered-rocksalt phase. The further TM interdiffusion and Mn^(3+) reduction are also revealed with multi-stage thermodynamics and kinetics. The mechanisms of phase transition and atom migrations as functions of temperature, time and atmosphere present important guidance on the synthesis in various-valence element containing oxides.

Chemical ordering and magnetic phase transitions in multiferroic BiFeO_(3)-AFe_(1/2)Sb_(1/2)O_(3)(A-Pb,Sr)solid solutions fabricated by a high-pressure

synthesisCeramic samples of BiFeO_(3)-based perovskite solid solutions with the highly ordered complex perovskites PbFe_(1/2)Sb_(1/2)O_(3)(PFS)and SrFe_(1/2)Sb_(1/2)O_(3)(SFS)were obtained using high-pressure synthesis at 4-6 GPa.Mössbauer studies revealed that BiFeO_(3)-SFS compositions are characterized by a larger compositional inhomogeneity as compared to BiFeO_(3)-PFS ones.In line with this result,concentration dependence of the magnetic phase transition temperature TN for BiFeO_(3)-SFS compositions is close to the TN(x)dependence for BiFeO_(3)solid solution with disordered perovskite PbFe_(1/2)Nb_(1/2)O_(3)(PFN).In contrast to this TN(x)dependence for BiFeO_(3)-PFS compositions nicely follows the theoretical TN(x)dependence calculated for the case of the ordered distribution of Fe3+and non-magnetic Sb^(5)+ions in the lattice(chemical ordering).

Structural Stability of Natural Magnesiochromite at High-Temperature-Pressure Conditions

The podiform chromitites in the Luobusha ophiolite have been thought to experience a very deep formation,but the maximum depth is still an open issue.Here,we have investigated the structural stability of natural magnesiochromite using the synchrotron-based powder X-ray diffraction and diamond anvil cells up to 48.6 GPa and 2450 K.The results have shown that spinel-type magnesiochromite first decomposes into corundum-type‘Cr_(2)O_(3)’+B1-type‘MgO’at 11–14 GPa and 1250–1450 K,then modified ludwigite(mLd)-type‘Mg_(2)Cr_(2)O_(5)’+corundum-type‘Cr_(2)O_(3)’at 14.3–20.5 GPa and 1300–2000 K,and finally CaTi_(2)O_(4)-type phase at 24.5 GPa.During the quenching procession from high-temperature-pressure conditions,the mLd-type phase appeared again and was kept at ambient conditions.We also obtained the isothermal equation states of spinel-type and CaTi_(2)O_(4)-type phases,revealing the composition effect on their elasticities.Based on the updated results,we propose chromitites could not experience pressure exceeding∼14.3 GPa(approximate maximum depth∼400 km)in the subduction-recycling genesis model.

Anomalous bond lengthening in compressed magnetic doped semiconductor Ba(Zn_(0.95)Mn_(0.05))_(2)As_(2)

Applying pressure has been evidenced as an effective method to control the properties of semiconductors,owing to its capability to modify the band configuration around Fermi energy.Correspondingly,structural evolutions under external pres-sures are required to analyze the mechanisms.Herein high-pressure structure of a magnetic doped semiconductor Ba(Zn_(0.95)Mn_(0.05))_(2)As_(2)is studied with combination of in-situ synchrotron X-ray diffractions and diamond anvil cells.The materials become ferromagnetic with Curie temperature of 105 K after further 20%K doping.The title material undergoes an isostruc-tural phase transition at around 19 GPa.Below the transition pressure,it is remarkable to find lengthening of Zn/Mn-As bond within Zn/MnAs layers,since chemical bonds are generally shortened with applying pressures.Accompanied with the bond stretch,interlayer As-As distances become shorter and the As-As dimers form after the phase transition.With further compres-sion,Zn/Mn-As bond becomes shortened due to the recovery of isotropic compression on the Zn/MnAs layers.

Approaching Ultimate Synthesis Reaction Rate of Ni-Rich Layered Cathodes for Lithium-Ion Batteries

Nickel-rich layered oxide LiNi_(x)Co_(y)MnzO_(2)(NCM,x+y+z=1)is the most promising cathode material for high-energy lithium-ion batteries.However,conventional synthesis methods are limited by the slow heating rate,sluggish reaction dynamics,high energy consumption,and long reaction time.To overcome these chal-lenges,we first employed a high-temperature shock(HTS)strategy for fast synthesis of the NCM,and the approaching ultimate reaction rate of solid phase transition is deeply investigated for the first time.In the HTS process,ultrafast average reaction rate of phase transition from Ni_(0.6)Co_(0.2)Mn_(0.2)(OH)_(2) to Li-containing oxides is 66.7(%s^(-1)),that is,taking only 1.5 s.An ultrahigh heating rate leads to fast reaction kinetics,which induces the rapid phase transition of NCM cathodes.The HTS-synthesized nickel-rich layered oxides perform good cycling performances(94%for NCM523,94%for NCM622,and 80%for NCM811 after 200 cycles at 4.3 V).These findings might also assist to pave the way for preparing effectively Ni-rich layered oxides for lithium-ion batteries.

High-temperature elemental segregation induced structure degradation in high-entropy fluorite oxide

Fluorite-structured oxides constitute an important category of oxides with a wide range of high-temperature applications.Following the concept of high entropy,high-entropy fluorite oxides(HEFOs)have showcased intriguing high-temperature application potential.However,unlocking this potential necessitates an assessment of their long-term stability under high-temperature conditions.In this study,we conducted a prolonged heat treatment at 1000℃on typical HEFO,specifically(CeHfZrGdLa)O_(x).After 100 h,high-intensity X-ray diffraction(XRD)revealed a transition from a single-phase fluorite to a multi-phase configuration.Further investigation by analytical electron microscoy(AEM)demonstrated that this degradation resulted from facilitated element diffusion and consequent escalating chemical fluctuation at high temperatures,leading to spontaneous segregation and separation of Ce and La elements,forming Ce-rich,La-poor,and La-rich phases.Notably,the La-rich phase spontaneously transformed from a fluorite structure(space group Fm3m)to a bixbyite structure(space group Ia3)at elevated temperatures,resulting in the appearance of superstructure reflection in XRD profiles and electron diffraction patterns.Despite the intricate phase decomposition,the energy band gap showed minimal variation,suggesting potential property stability of(CeHfZrGdLa)O_(x)across a broad range of compositions.These findings offer valuable insights into the future applications of HEFOs.

Superconducting properties of barium in three phases under high pressure from first principles

Electron-phonon coupling （EPC） in the three high-pressure phases of Ba is investigated using a pseudopotentlal planewave method based on density functional perturbation theory. The calculated values of superconducting critical temperature Tc of Ba-I and Ba-II under pressure are consistent well with the trends observed experimentally. Moreover, Ba-V is found to be superconducting with a maximum Tc exceeding 7.8 K at 45 GPa. With the increase of pressure, the values of Tc increase in Ba I and Ba-Ⅱ but the value of Tc decreases in Ba-V. For Ba-I at pressures below 2 GPa, the increases of logarithmic average frequency Oog and electron-phonon coupling parameters , both contribute to the enhancement of Tc. For all the three phases at pressures above 2 GPa, Tc is found to be primarily determined by Further investigation reveals that for all the three phases, the change in with pressure can be explained mainly by change in the phonon frequency. Thus for Ba-II and Ba-V, although they exhibit completely different superconducting behaviors, their superconductivities have the same origin; the pressure dependence of Tc is determined finally by the pressure dependence of phonon frequency.

Pressure-induced phase transition of wulfenite

The in-situ high-pressure structures of wulfenite have been investigated by means of angular dis- persive X-ray diffraction with diamond anvil cell and synchrotron radiation. In the pressure up to 22.9 GPa, a pressure-induced scheelite-to-fergusonite transition is observed at about 10.6 GPa. The pressure dependence for the lattice parameters of wulfenite is reported, and the axial compression coefficients Kao ----- -1.36 × 10^-3 GPa^-1 and Kc0 = -2.78× 10^-3 GPa^-1 are given. The room-temperature isothermal bulk modulus is also obtained by fitting the P-V data using the Murnaghan equation of state.

X-site doping in ABX_(3) triggers phase transition and higher T_(c) of the dielectric switch in perovskite

Material stability is always the key factor for applied materials especially the working environment that requires higher temperature sensitivity or temperature fluctuation range.In which,the stimulus-response perovskite materials are just sensitive to stability to ensure the accuracy and stability of the signals,in the applied devices of batteries and memory storage devices and so on.However,it is still a tremendous challenge to improve the stability of perovskite materials,and maintain reliability in the devices.Here,a novel ABX_(2)X'_(1)(X-site doping in an ABX_(3))compound[CEMP]-[CdBr_(2)(SCN)](1,CEMP=1-(2-chloro-ethyl)-1-methyl-piperidine)with remarkable high-temperature reversible dielectric switching behavior was proposed.The strategy of[SCN]^(−)doping in perovskite for improving the stability was successfully achieved.Meanwhile,the steric hindrance is increased while the energy barrier is also increased by replacing hydrogen with flexible groups,which leads to a high-temperature reversible phase transition.The new finding provides a new direction to enrich new applications and design ideas of perovskite materials.Especially the X-site strategy of doping or substitution in the ABX_(3),it will promote ingenious and perfect experimental results in material synthesis and performance improvement by chemistry disciplines.

Phase transitions in a hydrogen-rich compound: tetramethylsilane

High-pressure behavior of tetramethylsilane is investigated by synchrotron powder X-ray diffraction and Raman scattering at pressures up to 30 GPa and room temperature. Our results reveal the analogous phase transitions, though slight hysteresis for the certain phases. A new phase is found to appear at 4.2 GPa due to the disappeared Raman mode. These findings offer the possibility to understand the evolution of the H-H bonding with pressure in such hydrogen-rich compounds.

Studies of short-time and high-temperature annealing and magnetic property of LaFe_(11.4)Si_(1.6) compound

The LaFe11.4Si1.6 compounds are prepared by arc-melting and then annealed at different high temperatures from 1323 K （5 h） to 1623 K （2 h）. The powder X-ray diffraction （XRD） and microstructure observations show that large amount of 1：13 phase begins to appear in the LaFe11.4Si1.6 compound annealed at 1423 K （5 h）. In the temperature range from 1423 K to 1523 K, the α-Fe and LaFeSi phases rapidly decrease to form 1：13 phase. The LaFeSi phase is rarely observed by XRD when the as-cast compound is annealed at 1523 K （5 h）. With annealing temperature increasing to 1573 K, LaFeSi phase is detected again in LaFe11.4Si1.6 compound. In LaFe11.4Si1.6 compounds annealed at 1523 K （5 h）, at 1373 K （2 h）＋1523 K （5 h）, and 1523 K （7 h）＋1373 K （2 h）, the impurity phases including small amount of α-Fe and LaFeSi phase reduce in turn. The magnetic measurement shows that LaFe11.4Si1.6 compounds annealed by above three processes keep the first-order of magnetic transition behavior, and Tc are both at about 200 K. But the values of the maximal ASM（T, H） of has large difference, they are 9.94, 12.66, and 13.96 J/（kg.K） under a magnetic field of 0- 2 T, respectively.

Detailed structural,mechanical,and electronic study of five structures for CaF2 under high pressure

Detailed density functional theory(DFT)calculations of the structural,mechanical,thermodynamic,and electronicproperties of crystalline CaF2 with five different structures in the pressure range of 0 GPa–150 GPa are performed byboth GGA(generalized gradient approximation)-PBE(Perdew–Burke–Ernzerhof)and LDA(local density approximation)-CAPZ(Cambridge Serial Total Energy Package).It is found that the enthalpy differences imply that the fluorite phase→PbCl2-type phase→Ni2In-type phase transition in CaF2 occurs at PGGA1=8.0 GPa,PGGA2=111.4 GPa by usingthe XC of GGA,and PLDA1=4.5 GPa,PLDA2=101.7 GPa by LDA,respectively,which is consistent with previousexperiments and theoretical conclusions.Moreover,the enthalpy differences between PbCl2-type and Ni2In-type phases inone molecular formula become very small at the pressure of about 100 GPa,indicating the possibility of coexistence of twophase at high pressures.This may be the reason why the transition pressure of the second phase transition in other reportsis so huge(68 GPa–278 GPa).The volume changed in the second phase transition are also consistent with the enthalpydifference result.Besides,the pressure dependence of mechanical and thermodynamic properties of CaF2 is studied.Itis found that the high-pressure phase of Ni2In-type structure has better stiffness in CaF2 crystal,and the hardness of thematerial has hardly changed in the second phase transition.Finally,the electronic structure of CaF2 is also analyzed withthe change of pressure.By analyzing the band gap and density of states,the large band gap indicates the CaF2 crystal isalways an insulator at 0 GPa–150 GPa.

High-temperature dielectric switch and second harmonic generation integrated in a stimulus responsive material

Stimulus re s ponsive materials can provide a variety of desirable properties in one equipment unit,such as optoelectronic devices,data communications,actuators,memories,sensors and capacitors.However,it remains a large challenge to design such stimulus responsive materials,especially functional materials having both dielectric switch and second harmonic generation(SHG).Here,a new stimuli-responsive switchable material [(CH_(3))_(3)N(CH_(2))_(2)Cl]_(2)]Mn(SCN)_(4)(H_(2)O)_(2)] was discovered as a potential secondharmonic generation(SHG) dielectric switch.It is worth noting that it has SHG characteristics before and after undergoing reversible high-temperature phase transitions.In this work,we successfully refined the tetramethylammonium cation to obtain a quasi-spherical cation,which is tetramethylchloroethylamine(TMCEM) cation.By substituting H with a halogen,the increased steric hindrance of the molecular makes energy barrier increased,resulting in the reversible high-temperature phase transition.At the same time,the interactions of quasi-spherical cations and [Mn(SCN)_(4)(H_(2)O)_(2)]^(2-) anions affect a noncentrosymmetric structure to induce the SHG effect.These findings provide a new approach to design novel functional switch materials.

Structural transitions in Pb(In_(1/2)Nb_(1/2))O_(3) under pressure

Room-temperature Raman scattering and x-ray difraction measurements together with first principles calculations were employed to invetigate the behavior of disordered Pb(In_(1/2)Nb_(1/2))O_(3)(PIN)under pressure up to 50GPa.Raman spectra show broad bands but a peak near the 380cm^(-1) increases its intensity with pressure.The linewidth of the band at 550cm^(-1) also increases with pressure,while two of the Raman peaks merge above 6GPa.Above 16 GPa,we observe additional splitting of the band at 50cm^(-1).The pressure evolution of the diffraction patterns for PIN shows obvious Bragg peaks splitting above 16GPa;consistent with a symmetry lowering transition.The transition at 0.5 GPa is identified as a pseudo-cubic to orthorhombic(Pbam)structural change whereas the transition at 16GPa is istructure and associated with changes in linear compresibility and octahedral titling,and the transition at 30 GPa is associated to an orthorhombic to monoclinic change.First-principles calculations indicate that the Pbam structure is ground state with antiferrodisdortion consistent with experiment.

Effects of the excess iron on phase and magnetocaloric property of LaFe_(11.6*x)Si_(1.4) alloys

The effect of Fe on microstructure and magnetic thermal performance of LaFel 1.6.xSil.4 alloys were studied by X-ray dif- fraction （XRD）, scanning electron microscopy （SEM）, energy dispersive spectroscopy （EDS）, and vibrating-sample magnetometer （VSM）, respectively. The results showed that the excess Fe would make the 1：13 phase reduce in proportion and the easy corrosion phase LaFeSi phase disappear in LaFelL6＊xSil.4 alloys. The LaFel 1.6.xSil.4 alloys kept the first order magnetic phase transition, and the maximum isothermal magnetic entropy changed and the relative cooling power reached the maximum in LaFel 1.6,xSil.4 alloys with x=1.05 and 1.1, respectively.

ertical morphotropic phase boundary in lead-free piezoelectric ceramics(K,Na,Li)NbO_(3)-BaZrO_(3)-(La,Na)TiO_(3) system

A morphotropic phase boundary(MPB)with temperature-independent behavior,the so-called vertical MPB was investigated in lead-free(K,Na,Li)NbO_(3)–BaZrO_(3)–(La,Na)TiO_(3)ternary ceramic system.The specimens were synthesized by a conventional solid-state reaction method,and their crystal structures as well as their MPB were determined from X-ray diffraction patterns measured from room temperature to 300℃.The vertical MPB composition was determined to be 0.9025(K_(0:45)Na0:5Li_(0:05))NbO_(3)–0.09BaZrO_(3)–0.0075(La,Na)TiO_(3)and the Curie temperature was found to be about 195℃.It was successfully confirmed that ceramic samples of this system could be sintered in a reducing atmosphere.For lead-free piezoceramic applications of multilayer actuators using Ni inner electrodes,the results obtained in this work have important practical implications.

High pressure X-ray diffraction study of CaMnO_3 perovskite

Using a diamond anvil cell device and synchrotron radiation,the in-situ high-pressure structure of CaMnO3 has been investigated.In the pressure up to 36.5 GPa,no pressure-induced phase transition is observed.The pressure dependence on the lattice parameters of CaMnO3 is reported,and the relationship of the axial compression coefficients is βa 〉 βc 〉 βb.The isothermal bulk modulus K298=224（25） GPa is also obtained by fitting the pressure-volume data using the Murnaghan equation of state.

High pressure X-ray diffraction study of SrMnO_3 perovskite

Using a diamond anvil cell device and synchrotron radiation, the in-situ high-pressure structure of SrMnO 3 has been investigated. At pressure up to 28.6 GPa, no pressure-induced phase transition is observed. The lattice parameters as a function of pressure is reported, and the relationship of the axial compression coefficients is β a 〉 β c . The isothermal bulk modulus K 298 =266（4） GPa is also obtained by fitting the pressure- volume data using the Murnaghan equation of state.