Pressure-induced Structural Phase Transition Research Articles

Pressure-induced structural and electronic phase transitions in GaGeTe

Pressure-induced structural and electronic phase transitions in GaGeTe

Artificial neural network for deciphering the structural transformation of condensed ZnO by extended x-ray absorption fine structure spectroscopy

Pressure-induced structural phase transitions play a pivotal role in unlocking novel material functionalities and facilitating innovations in materials science. Nonetheless, unveiling the mechanisms of densification, which relies heavily on precise and comprehensive structural analysis, remains a challenge. Herein, we investigated the archetypal B4 → B1 phase transition pathway in ZnO by combining x-ray absorption fine structure (XAFS) spectroscopy with machine learning. Specifically, we developed an artificial neural network (NN) to decipher the extended-XAFS spectra by reconstructing the partial radial distribution functions of Zn–O/Zn pairs. This provided us with access to the evolution of the structural statistics for all the coordination shells in condensed ZnO, enabling us to accurately track the changes in the internal structural parameter u and the anharmonic effect. We observed a clear decrease in u and an increased anharmonicity near the onset of the B4 → B1 phase transition, indicating a preference for the iT phase as the intermediate state to initiate the phase transition that can arise from the softening of shear phonon modes. This study suggests that NN-based approach can facilitate a more comprehensive and efficient interpretation of XAFS under complex in-situ conditions, which paves the way for highly automated data processing pipelines for high-throughput and real-time characterizations in next-generation synchrotron photon sources.

A pressure-induced superhard SiCN4 compound uncovered by first-principles calculations.

Silicon-carbon-nitride (Si-C-N) compounds are a family of potential superhard materials with many excellent chemical and physical properties; however, only SiCN, Si2CN4 and SiC2N4 were synthesized. Here, we theoretically report a new SiCN4 compound with P41212, Fdd2 and R3̄ structures by first-principles structural predictions based on the particle swarm optimization algorithm. Pressure-induced structural phase transitions from P41212 to Fdd2, and then to the R3̄ phase were determined at 2 GPa and 249 GPa. By comparing enthalpy differences with 1/3Si3N4 + C + 4/3N2, it was found that these structures tend to decompose at ambient pressure. However, with the increase of pressure, the enthalpy differences of Fdd2 and R3̄ structures turn to be negative and they can be stabilized at a pressure of more than 41 GPa. They are also dynamically stable as no imaginary frequencies were found in their stabilized pressure ranges. The calculated band gap is 4.37 eV for P41212, 3.72 eV for Fdd2 and 3.81 eV for the R3̄ phase by using the Heyd-Scuseria-Ernzerhof (HSE06) method and the estimated Vickers hardness values are higher than 40 GPa by adopting the elastic modulus based hardness formula, which confirmed their superhard characteristics. These results provide significant insights into Si-C-N systems and will inevitably promote the future experimental works.

Experimental observation of two-dimensional phase in compressed FeF2

Iron difluoride (FeF2) has attracted considerable attention for its physical characteristics and practical applications, and its compression behaviors usually play a key role in the in-depth understanding of this compound. Since its high-pressure crystal structure evolution determining a more profound comprehension remains disputable, we carried out extensive experiments to focus on the pressure-induced structural phase transitions of FeF2. Through in situ high-pressure synchrotron x-ray diffraction measurements, we not only confirmed a reported high-pressure orthorhombic Pbca phase at 11 GPa but also identified an interesting two-dimensional structure with hexagonal close packed symmetry (P-3m1) that appears above 25 GPa at room temperature. Furthermore, the spontaneous strain fitting and electronic transport measurements suggest that its ambient rutile-type structure (P42/mnm) evolves into an orthorhombic structure (Pnnm) through a second-order phase transition at 5 GPa. These experimental results elaborate on the pressure-induced phase transitions of FeF2 on the order of P42/mnm → Pnnm → Pbca → P-3m1, shedding light on a rare three-dimensional to two-dimensional configuration transition in difluorides.

Pressure-induced structural evolution to a nearly perfect kagome lattice in β-Mn2(OH)3Cl nanosheets

The frustrated magnets exhibiting kagome geometries and the investigation of their structure-property relationships have garnered substantial attention as potential candidates for quantum spin liquid (QSL). In this study, β-Mn2(OH)3Cl nanosheets with distorted kagome geometries were synthesized via a solid-state reaction, and low-temperature magnetic measurements revealed a spin-glass-like magnetic phase transition around 40 K in the frustrated β-Mn2(OH)3Cl. A pressure-induced structural phase transition was further realized by employing in situ synchrotron X-ray diffraction, leading to a hexagonal crystal structure with a nearly perfect kagome lattice of magnetic Mn2+ ions. High-pressure Raman and UV–vis absorption measurements indicates that the topological evolution can be attributed to the synergistic effects of pressure driven internal hydrogen bonds and the intrinsic Jahn-Teller effects. This study provides a strategy for synthesizing candidate compounds of QSL and sheds light on the mechanism underlying the topological evolution of kagome lattices under high pressure.

Pressure-induced reversible structural phase transitions and metallization in GeTe under hydrostatic and non-hydrostatic environments up to 22.9 GPa

The pressure-dependent vibrational and electrical transport properties of GeTe have been investigated in a diamond anvil cell through in-situ Raman spectroscopy and electrical conductivity measurements under hydrostatic and non-hydrostatic environments up to 22.9 GPa. Upon compression, two structural transformations from rhombohedral to cubic NaCl-type to orthorhombic GeTe occurred at 3.2 GPa and 12.3 GPa under non-hydrostatic condition. Similarly, two corresponding phase transitions were detected at much higher pressures of 5.0 GPa and 15.4 GPa under hydrostatic condition. Additionally, a 3.3 GPa of electronic transition accompanying by the rhombohedral to cubic NaCl-type transition was characterized by the variable-temperature electrical conductivity experiments. Upon decompression, the recoverable Raman spectra and resumable electrical conductivity suggested that the structural and electronic transitions of GeTe were reversible. The reversibility was further confirmed by the microscopic structural observations from high-resolution transmission electron microscopy, fast Fourier transform and atomic force microscopy.

First-principles study of structural phase transitions and metallization of XPSe3 (X = Fe, Mn) under high pressure

The pressure-induced structural phase transition and metallization of FePSe3 and MnPSe3 are investigated from ambient pressure to 40 GPa by first-principles calculation. FePSe3 and MnPSe3 undergo reversible structural transitions from R3¯ structure to C2/m structure and then to P3¯1m structure. The structural phase transitions of FePSe3 are at about 6 GPa and 13 GPa, while the pressure points are at approximately 13 GPa and 25 GPa for MnPSe3, reflecting from pressure-dependent enthalpy calculation, cell volume collapses, and sudden changes of lattice parameters. The computed metallization transition is also observed at around 8 GPa and 16 GPa owing to energy-band closure for FePSe3 and MnPSe3, respectively. The metallic character of XPSe3 is strengthened with increasing pressure based on the electronic energy band and electron density of states. The layer sliding of atoms is revealed using the P2-P3 atom pair of XPSe3 during structural phase transitions. The paper is conducive to considering the electronic structure and metallization of transition metal thiophosphates XPSe3-type family under extreme conditions.

Pressure induced structural phase transitions in calcium halofluorides

Density Functional Theory (DFT) is a powerful tool to investigate the pressure-induced structural phase transitions in materials. We predicted that CaClF and CaBrF undergo a structural transition from P4/nmm to Pnma at 57 GPa and 135 GPa, respectively, while no phase transition is observed for CaIF until the maximum studied pressure of 200 GPa. The electronic structure calculations reveal that the valence band of CaXF are separated into two manifolds due to electronegativity difference between F and X (Cl, Br, I), the manifold close to Fermi level is mainly originated from p-states of X while the well below manifold is derived from the 2p-states of F. The highest electronegativity of F atom makes the difference between alkaline-earth halofluorides and dihalides from their electronic structure, which determines their application as storage phosphors rather than highlight output scintillators similar to alkaline-earth dihalides.

Pressure-Induced Reversible and Irreversible Multistate Switching in NiAs-Type Chromium Selenides

Materials capable of switching in multiple states under external stimuli have garnered extensive attention in the field of memory devices and switches. The coupling of various switching properties is of paramount significance to the creation of multifunctional devices. Herein, we report the pressure-induced multiswitching behaviors of both the structural and physical properties in two chromium selenides, CrSe and Cr2Se3. Comprehensive high-pressure characterizations reveal the collaborative occurrence of pressure-induced structural phase transitions, spin-crossover, metallization, and n–p conduction-type switching in both compounds. Upon compression, Cr2Se3 demonstrates an unexpected increase in resistivity and band gap, which is associated with the disordering of the self-intercalation structure. Of particular interest is that due to the dimensional differences in crystal structures, the photoelectric properties of the two decompressed samples are inversely regulated after pressure treatment. Notably, the band gap of Cr2Se3 is pronouncedly broadened after decompression due to the partially irreversible disorder in the structure. These results demonstrate that pressure engineering can regulate the photoelectric properties of materials effectively and flexibly, serving as a potential foundation for fabricating innovative pressure-responsive multifunctional devices.

High-pressure effect on the superconductivity of NaAlGe and pressure-induced structural phase transition

The structural, electronic, phonon, and electron–phonon properties of NaAlGe have been investigated under high pressure by means of density-functional theory simulations. The calculated electronic structure and density of states reveal that the electronic states near the Fermi level, which are responsible for electrical conductivity, are mostly composed of Ge 4p states. The largest contribution to the average electron–phonon coupling parameter is from Ge-related vibrations, and this parameter is calculated to be λ∼ 0.609. The superconducting critical temperature at ambient pressure is calculated to be Tc = 2.31 K. This temperature agrees with the previously experimentally obtained value of 1.80 K. The electronic density of states at the Fermi energy, λ, and Tc decrease as pressure is increased, and superconductivity is suppressed at 12 GPa. We also report the phonon dispersion at different pressures showing that NaAlGe develops a dynamical instability at 13 GPa favoring a structural phase transition Based on enthalpy calculations the crystal structure of the high-pressure phase has been proposed to be orthorhombic and described by space group Pnma. This phase does not exhibit superconductivity. The pressure dependence of unit-cell parameters and Raman- and infrared-active phonons of the low-pressure and high-pressure phase is also reported.

Pressure-Induced Structural Phase Transition of Co-Doped SnO2 Nanocrystals

Co-doped SnO2 nanocrystals (with a particle size of 10 nm) with a tetragonal rutile-type (space group P42/mnm) structure have been investigated for their use in in situ high-pressure synchrotron angle dispersive powder X-ray diffraction up to 20.9 GPa and at an ambient temperature. An analysis of experimental results based on Rietveld refinements suggests that rutile-type Co-doped SnO2 undergoes a structural phase transition at 14.2 GPa to an orthorhombic CaCl2-type phase (space group Pnnm), with no phase coexistence during the phase transition. No further phase transition is observed until 20.9 GPa, which is the highest pressure covered by the experiments. The low-pressure and high-pressure phases are related via a group/subgroup relationship. However, a discontinuous change in the unit-cell volume is detected at the phase transition; thus, the phase transition can be classified as a first-order type. Upon decompression, the transition has been found to be reversible. The results are compared with previous high-pressure studies on doped and un-doped SnO2. The compressibility of different phases will be discussed.

Compressive Symbol: A New Way to Evaluate the High-Pressure Behaviors of Energetic Tetrazole Materials.

Energetic materials may transit to different phases or decompose directly under compression. Their reactivity in the explosions can be evaluated by their high-pressure induced behaviors, including polymorphism or phase transition. Here, we applied DFT methods to understand high-pressure behaviors of four typical tetrazole derivate crystals, including 5-aminotetrazole (ATZ), 1,5-aminotetrazole (DAT), 5-hydrazinotetrazole (HTZ), and 5-azidotetrazole (ADT), under the gradually increased pressure from ambient pressure to 200 GPa. In response to the extreme-high pressures, the performances are dominated by compressibility of crystals, reflected by compressive symbols on the basis of the molecular orientation in crystals. The crystal with weak compressibility (large symbol) generally dissociates, triggered by cleavage of weak bonds. However, the crystal with low compressive symbol is generally corresponding to a pressure-induced structural transformation or phase transition.

Pressure-induced Structural Phase Transition and New Superconducting Phase in UTe2

We report on the crystal structure and electronic properties of the heavy fermion superconductor UTe2 at high pressure up to 11 GPa, as investigated by X-ray diffraction and electrical resistivity experiments. The X-ray diffraction measurements under high pressure using a synchrotron light source reveal anisotropic linear compressibility of the unit cell up to 3.5 GPa, while a pressure-induced structural phase transition is observed above PO–T ∼ 3.5–4 GPa at room temperature, where the body-centered orthorhombic crystal structure with the space group Immm changes into a body-centered tetragonal structure with the space group I4/mmm. The molar volume drops abruptly at PO–T, while the distance between the first-nearest neighbor of U atoms, dU–U, increases, implying a switch from the heavy electronic states to the weakly correlated electronic states. Surprisingly, a new superconducting phase at pressures higher than 7 GPa was detected at Tsc > 2 K with a relatively low upper-critical field, Hc2(0). The resistivity above 3.5 GPa, thus, in the high-pressure tetragonal phase, shows a large drop below 230 K, which may also be related to a considerable change from the heavy electronic states to the weakly correlated electronic states.

Structural and electronic properties of Weyl semimetal WTe2 under high pressure

The structural and electronic properties of WTe2 are studied from ambient pressure to 30.0 ​GPa. The pressure-induced structural phase transition is found from Td phase to 1T′ phase above 10.0 ​GPa by lattice offset, which is also reflected at approximately 11.2 ​GPa based on the discontinuous electrical parameters. A pair of hole wave and electron wave packets of Td phase gradually overlap revealing the reversible Td-to-1T′ phase structural transition. WTe2 is observed to undergo semimetal-to-semiconductor transition owing to the calculated energy band up to 15 ​GPa, which is also observed at 11.2 ​GPa according to the resistivity-temperature curves under compression and decompression conditions. The electronic density of states at the Fermi level is mainly contributed by the d orbital of W and the p and s orbital of Te. The photoconductivity property is shown by the theoretical and experimental methods.

Pressure-Induced Structural Phase Transition and Enhanced Interlayer Coupling in Two-Dimensional Ferromagnet CrSiTe3

The two-dimensional van der Waals ferromagnetic semiconductor CrSiTe3 has attracted growing interest as an intrinsic topological magnet. Both superconductivity and enhancement of ferromagnetism, usually competing for orders, have been observed in CrSiTe3 at high pressure. However, the high-pressure structure of CrSiTe3 is still unclear, setting obstacles in understanding pressure-induced novel physics. Here, combining the Raman spectra and first-principles calculations, the structure of CrSiTe3 at high pressure has been clarified. The interlayer breathing mode located at ∼42.1 cm-1 has been observed for the first time in CrSiTe3 by ultralow-frequency Raman spectroscopy at high pressure. Theoretical calculations confirm a phase transition from the R3̅ phase to the R3 phase accompanying noticeable enhancement of the Curie temperature. Our results highlight ultralow-frequency Raman spectroscopy combined with high pressure for detecting and modulating the structure and interlayer coupling of two-dimensional materials.

Effects of High Pressure on the Bandgap and the d–d Crystal Field Transitions in Wolframite NiWO4

The pressure effects on the optical and structural properties of NiWO4 have been studied experimentally and theoretically. The fundamental bandgap decreases with a pressure coefficient of −12.0 ± 0.2 meV/GPa. Meanwhile, the Ni2+ d–d transition energies increase at a rate of 7.4–14.8 meV/GPa. Therefore, the energy differences between the fundamental band and the Ni2+ d–d transition bands gradually decrease under pressure, which is beneficial to improve its optical performance. These optical phenomena are associated with structural variations. The shrinkage of the WO6 octahedron enhances the hybridization between the W 5d and O 2p orbitals, resulting in bandgap reduction. The pressure-induced enhancement of the NiO6 octahedral symmetry increases the crystal field splitting, thereby yielding increases in the Ni2+ d–d intraband transition energies. Besides, a pressure-induced structural phase transition is also observed around 20.0 GPa by both angle-dispersive synchrotron X-ray diffraction (ADXRD) and Raman experiments. This study provides valuable insight into the electron–lattice coupling of NiWO4 under compression and an effective way to modulate the electronic structure and optical properties of isomorphic wolframite materials.

Pressure-induced structural phase transitions in natural monazite

The behavior of natural monazite $(\mathrm{La},\phantom{\rule{0.16em}{0ex}}\mathrm{Ce},\phantom{\rule{0.16em}{0ex}}\mathrm{Nd})\mathrm{P}{\mathrm{O}}_{4}$ at high pressure is investigated by Raman spectroscopy. Changes in the Raman spectra indicate a phase transition from monazite to a post-monazite phase. Single-crystal x-ray diffraction measurements of the decompressed sample reveal that the post-monazite phase has a distorted barite-type structure with space group $P{2}_{1}/n$. This phase transition is irreversible under quasihydrostatic conditions, and is reversible under nonhydrostatic conditions. Therefore, it is expected that the post-monazite phase cannot be found as a metastable phase at ambient conditions in impact craters due to nonhydrostatic conditions during shock metamorphism, supporting recent mineralogical observations in impact craters.

Pressure-Induced Structural Phase Transitions in the Chromium Spinel LiInCr4O8 with Breathing Pyrochlore Lattice

This study reports high-pressure structural and spectroscopic studies on polycrystalline cubic chromium spinel compound LiInCr4O8. According to pressure-dependent X-ray diffraction measurements, three structural phase transitions occur at ∼14 GPa, ∼19 GPa, and ∼36 GPa. The first high-pressure phase is indexed to the low-temperature tetragonal phase of the system which coexists with the ambient phase before transforming to the second high-pressure phase at ∼19 GPa. The pressure-dependent Raman and infrared spectroscopic measurements show a blue-shift of the phonon modes and the crystal field excitations and an increase in the bandgap under compression. During pressure release, the sample reverts to its ambient cubic phase, even after undergoing multiple structural transitions at high pressures. The experimental findings are compared to the results of first principles based structural and phonon calculations.

Phase transition and bond symmetrization associated with noble gas bond in XeO3

The pressure-induced structural phase transition of XeO3 is studied by first principle calculations. The transition from P212121 to Pnma accompanied by a drastic reduction of volume is found at 2.18 GPa. The symmetrilized Xe−O2 bonds give rise to the better symmetry of high pressure phase. O-hopping between different possible local minima and the motion of Xe along the y axis may be responsible for phase transition. Results of electron localization function indicate that three ipsilateral Xe−O bonds lead to a lone-pair contour of Xe6+.

Pressure-Induced Abnormal Electrical Transport Transition from Pure Electronic to Mixed Ionic–Electronic in Multiferroic BiFeO3 Ceramics

Pressure-induced structural changes could induce changes in transport properties and lead to a better understanding of the structure–property relationship. The evolution of the carrier transport properties of BiFeO3 (BFO) ceramics under a high pressure was investigated through impedance spectroscopy measurements at room temperature combined with first-principles calculations. A pressure-induced abnormal transition from pure electronic to mixed ionic–electronic was found in the BFO ceramics Cmmm and Pnma phases at 7.67 and 11.01 GPa, respectively. The pressure-induced structural phase transition from the R3c phase to Cmmm and then to Pnma was responsible for the change in electrical transport behavior from pure electronic to mixed ionic–electronic conduction, accompanied by a decrease in ionic resistance. The calculations of electronic structures and electron localization function from 1 atm to 40 GPa indicated that the ionic conduction in the Pnma phase resulted from the weakened Coulomb screen of the localized electron background to O2– between Bi3+ and O2–. This work provides a critical insight into the understanding of the relationship between structure and conduction and facilitates the application of ferroelectric materials in photoelectric fields.