Pressure-induced Phase Transition Research Articles

Iso-structural phase transition in pyrochlore iridates (Sm1-xBix)2Ir2O7 (x = 0, 0.02, and 0.10): High-pressure Raman and X-ray diffraction studies.

The pyrochlore iridates, A2Ir2O7, show a wide variety of structural, electronic, and magnetic properties controlled by the interplay of different exchange interactions, which can be tuned by external pressure. In this work, we report pressure-induced iso-structural phase transitions at ambient temperature using synchrotron-based X-ray diffraction (up to ∼ 20 GPa) and Raman-scattering measurements (up to ∼ 25 GPa) of the pyrochlore series (Sm1-xBix)2Ir2O7 (x = 0, 0.02, and 0.10). Our Raman and X-ray data suggest an iso-structural transition in Sm2Ir2O7 at Pc ∼ 11.2 GPa, associated with the rearrangement of IrO6 octahedra in the pyrochlore lattice. The transition pressure decreases to ∼ 10.2 and 9 GPa for x = 0.02 and 0.10, respectively. For all the samples, the linewidth of three phonons associated with Ir-O-Ir (A1g and Eg) and Ir-O (T24g ) vibrations show anomalous decrease up to Pc, due to decrease in electron-phonon interaction.

Pressure-induced phase transitions of ZrAl2 from first-principles calculations

Although ZrAl2 has been extensively studied, its structural features and properties under high pressures remain unclear. Using the CALYPSO structural search method combined with first-principles calculations, we investigated the structural evolution and mechanical stability of ZrAl2 at high pressures. Our research reveals that at 198 GPa, ZrAl2 undergoes a phase transition from the P63/mmc phase to the Pmmm phase. This transition results in a volume collapse of 2.1%, indicating a first-order phase change. A comprehensive analysis of the elastic constants and phonon spectra confirms the structural stability of four new phases of ZrAl2. Our research findings provide a comprehensive view of the structural evolution of ZrAl2 under high pressure. This valuable information enhances the understanding of the physical and chemical properties of C14-type ZrAl2 when subjected to high-pressure conditions.

Near-Full-Spectrum Emission Realized in a Single Lead Halide Perovskite across the Visible-Light Region.

The engineering of tunable photoluminescence (PL) in single materials with a full-spectrum emission represents a highly coveted objective but poses a formidable challenge. In this context, the realization of near-full-spectrum PL emission, spanning the visible light range from 424 to 620 nm, in a single-component two-dimensional (2D) hybrid lead halide perovskite, (ETA)2PbBr4 (ETA+ = (HO)(CH2)2NH3+), is reported, achieved through high-pressure treatment. A pressure-induced phase transition occurs upon compression, transforming the crystal structure from an orthorhombic phase under ambient conditions to a monoclinic structure at high pressure. This phase transition driven by the adaptive and dynamic configuration changes of organic amine cations enables an effective and continuous narrowing of the bandgap in this halide crystal. The hydrogen bonding interactions between inorganic layers and organic amine cations (N-H…Br and O-H…Br hydrogen bonds) efficiently modulate the organic amine cations penetration and the octahedral distortion. Consequently, this phenomenon induces a phase transition and results in red-shifted PL emissions, leading to the near-full-spectrum emission. This work opens a possibility for achieving wide PL emissions with coverage across the visible light spectrum by employing high pressure in single halide perovskites.

Pressure-induced optical anisotropy of HfS2

The effect of pressure on Raman scattering (RS) in bulk HfS2 is investigated under hydrostatic and non-hydrostatic pressure conditions. The RS line shape does not change significantly in the hydrostatic regime up to P = 9.6 GPa, showing a systematic blueshift of the spectral features. In a non-hydrostatic environment, seven peaks appear in the spectrum at P = 7 GPa, which dominate the RS line shape up to P = 10.5 GPa. The change in the RS line shape manifests a pressure-induced phase transition in HfS2. The simultaneous observation of both low-pressure (LP) and high-pressure (HP) related RS peaks suggests the coexistence of two different phases over a wide pressure range. It is found that the HP-related phase is metastable and persists during the decompression cycle down to P = 1.2 GPa, while the LP-related features eventually recover at even lower pressure. The angle-resolved polarized RS performed under P = 7.4 GPa revealed a strong in-plane anisotropy of both the LP-related A1g mode and the HP peaks. The anisotropy is related to the possible distortion of the structure induced by the non-hydrostatic component of the pressure. The results are explained in terms of a distorted Pnma phase as a possible pressure-induced phase of HfS2.

A search for pressure-induced phase transition in the layered perovskite-like Pr2Ti2O7

In our study, we present comprehensive findings on the structural properties of Pr2Ti2O7 across a broad pressure range of 0-30GPa. Neutron diffraction experiments, conducted under ambient conditions, offer crucial structural insights into the initial monoclinic phase with the P21 space group. As pressure increased, a significant phase transition to the monoclinic P21/m phase occurred at 13.8GPa. Structural data analysis from X-ray diffraction highlights the essence of this transition, identifying it as the tilting of Ti-O6 octahedra. High-pressure Raman spectroscopy data unequivocally confirms the phase transition, detecting anomalies in the baric dependencies of some vibration modes of Pr2Ti2O7 and the emergence of new modes in the Raman spectra within the pressure region associated with the phase transition. The analysis of these novel vibration modes points to alterations in the Ti-O6 octahedra, emphasizing the pivotal role played by Ti4+ and O2- ions in the mechanism of the pressure-driven phase transition.

Pressure-induced temperature-driven phase transition and compressibility studies on nanocrystalline and bulk -U3O8 at extreme conditions of pressure and temperature

The study investigates the structural transition pathways of U3O8 under varying temperature and pressure conditions, focusing on both bulk and nanocrystalline forms. The bulk U3O8 is known to undergo reversible phase transitions to a hexagonal structure at temperatures above 150°C and irreversible transitions to a fluorite structure under pressure at ambient temperature. High-pressure XRD experiments reveal a significant decrease in transition pressure for the hexagonal to fluorite phase transition in bulk U3O8, with the HT-hex phase exhibiting a bulk modulus of 155 ± 21 GPa at 450°C. In 82 nm nanocrystalline U3O8, the transition from orthorhombic to hexagonal phase is reversible up to 1.0 GPa and 500°C but becomes irreversible above 1.7 GPa. The bulk modulus of the hexagonal phase of nanocrystalline U3O8 is estimated to be 168±12 GPa and 146±16 GPa at 400°C and 500°C, respectively. The findings highlight the complexity of structural transformations in U3O8 and their dependence on temperature and pressure, offering insights valuable for materials science and nuclear reactor engineering.

Band-Gap Narrowing and Electric Transport Regulation of Hybrid Perovskites via Pressure Engineering.

Lead-free organic-inorganic hybrid perovskites are one class of promising optoelectronic materials that have attracted much attention due to their outstanding stability and environmentally friendly nature. However, the intrinsic band gap far from the Shockley-Queisser limit and the inferior electrical properties largely limit their applicability. Here, a considerable band-gap narrowing from 2.43 to 1.64 eV with the compression rate up to 32.5% is achieved via high-pressure engineering in the lead-free hybrid perovskite MA3Sb2I9. Meanwhile, the electric transport process changes from the initial interaction of both ions and electrons to only the contribution of electrons upon compression. The alteration in electrical characteristics is ascribed to the vibration limitation of organic ions and the enhanced orbital overlap, resulting from the reduction of the Sb-I bond length through pressure-induced phase transitions. This work not only systematically investigates the correlation between the structural and optoelectronic properties of MA3Sb2I9 but also provides a potential pathway for optimizing electrical properties in lead-free hybrid perovskites.

Exploring structural phase transition, electronic and optical characteristics of optoelectronic phosphides XSiP2 (X = Mg, Cd, and Zn) through First principle computation.

The present study reports the properties of pressure-induced phase transition, electronic and optical of phosphides XSiP2 under pressure in chalcopyrite, sodium chloride (rock salt), and Wurtzite phases. The study shows the chalcopyrite phase as the most stable phase among the other studied phases. The obtained structural parameters in the chalcopyrite and rock-salt phases reasonably agree with the literature. The computed band structures revealed a semiconductor behavior in chalcopyrite structure and metallic behavior for rock- salt and wurtzite structures. In the energy range of 0 to 30eV, optical parameters such as the real and imaginary parts of the dielectric constant, refractive index, and reflectivity are calculated and compared with existing data. Our optical properties findings are predictive for the rock-salt and wurtzite phases. Since no results are available in the literature, these results may serve as references for other theoretical and experimental studies. The calculations are performed by employing the "full-potential linearized augmented plane wave (FP-LAPW) method within density functional theory (DFT)."

VIBRATIONAL AND X-RAY MEASUREMENTS OF La2Ti2O7 UNDER HIGH PRESSURE CONDITION

The present study focuses on investigating the impact of high-pressure conditions on the crystal structure and vibration spectra of the perovskite-like layered compound La2Ti2O7. To this end, X-ray diffraction and Raman spectroscopy techniques were employed to observe the behavior of the compound under pressure levels up to 30 GPa. The neutron diffraction at ambient pressure confirms that the structure of La2Ti2O7 is monoclinic P21. The results indicate that when the pressure attains 17.3 GPa, the original monoclinic phase of P21 symmetry undergoes a phase transition to the monoclinic phase of P2 symmetry. The observed pressure-induced phase transitions in La2Ti2O7 are associated with anomalous changes in both the unit cell parameters and the vibrational modes. Additionally, the study obtained the baric dependences of lattice parameters, unit cell volume and vibration frequencies, which were used to calculate the bulk modules for the initial and pressure-induced phases of La2Ti2O7.

Barocaloric effect in a Gay-Berne liquid crystal.

A coarse-grained molecular Monte Carlo simulation of the barocaloric effect in a model Gay-Berne liquid crystal is presented, following the so-called indirect approach wherein the caloric response is obtained from thermodynamic arguments applied to the simulated equilibrium relation between pressure, density, and temperature. From simulation, the magnitude of the effect across the isotropic-nematic and nematic-smectic phase transitions is estimated, together with the heat exchanged outside these transitions, in order to assess its potential for novel cooling and heat pumping applications. Under adiabatic conditions, pressure-induced phase transitions are predicted to result in a temperature variation of a few degrees Kelvin. As a by-product of the simulation, an approximate partial phase diagram of the Gay-Berne fluid under study is also obtained.

Unveiling the pressure-induced scheelite to M′-fergusonite phase transition in NaCe(MoO4)2

Sodium-cerium molybdate, NaCe(MoO4)2, belongs to the family of double alkaline rare-earth molybdate, and it holds significant importance across various technological domains, such as environmental remediation and energy conversion. Despite its importance, the behavior of NaCe(MoO4)2 under high-pressure conditions remains unexplored. This study uses synchrotron x-ray diffraction and Raman spectroscopy to investigate NaCe(MoO4)2in situ under high-pressure conditions. We observed a pressure-induced phase transition from the scheelite to the M′-fergusonite structure type on a double molybdate at approximately 10 GPa. These findings contribute to a deeper understanding of the structural stability of NaCe(MoO4)2 and shed light on the broader field of high-pressure studies of double molybdates.

Cooperative Octahedral Tilt Modes Drive Coexisting Displacive and Order–Disorder Pressure-Induced Phase Transitions in MAPbBr3

Cooperative Octahedral Tilt Modes Drive Coexisting Displacive and Order–Disorder Pressure-Induced Phase Transitions in MAPbBr₃

Raman spectroscopy study on terephthalamide crystal at high pressures

In this study, we have investigated the structural stability of terephthalamide (TPA) crystal at pressure from ambient to 15 GPa in the diamond anvil cell at room temperature by Raman spectroscopy. Assignment for the Raman vibration modes of TPA crystal at ambient conditions has been performed based on the density functional theory (DFT) calculations. Pressure-induced structural transition was monitored using in-situ Raman spectroscopy. Remarkable changes (including the appearance of new Raman peaks, disappearance of original Raman bands, discontinuous changes in the pressure dependence of some Raman wavenumbers at different pressures) in Raman spectra were observed at approximately 1.3 and 5.2 GPa, provided clear evidences for two pressure-induced phase transitions: phase I to phase II at ∼1.3 GPa, phase II to phase III at ∼5.2 GPa.

Ab-initio investigation of the structural, electronic and optical properties of CsPbBr3 perovskite under pressure using the DFT-1/2 method

Pressure-induced phase transitions in metal halide perovskites lead to significantly different material properties and offer great potential for diverse applications. The electronic, structural, and optical properties of Cesium lead bromide (CsPbBr3) crystals are investigated using density functional theory (DFT) to draw an integrated picture of orbital morphology, absorption spectra, and band gap values. Spin-orbit coupling and DFT-1/2 correction are used to gain a better insight into electronic properties and band splitting in the cubic phase. Calculations of pressure-induced phase transitions, electronic band gap engineering, and manipulation of optical absorption edges of CsPbBr3 are conducted. In the cubic and tetragonal crystal lattices, a band gap closure and opening occurs demonstrating a Dirac cone upon application and increase of pressure. Indeed, in the tetragonal lattice of CsPbBr3, a topological band occurs. Orthorhombic perovskite crystal lattice undergoes successive direct-indirect and indirect-direct band gap transitions, followed by a space group change at extreme pressures. However, under pressure, orthorhombic non-perovskite lattice experiences a sudden band gap breakdown. Phase and band gap transitions are explained by orbital hybridizations and structural symmetry evolution (e.g., bond length contraction/dilation and octahedral cage rotation/distortion). These results provide comprehensive guidelines for further experimental studies on pressure engineering, advanced photovoltaic and optoelectronic applications, discovering and understanding new topological band structures of perovskite materials.

A comparative study of the high-pressure structural stability of zirconolite materials for nuclear waste immobilisation

We present a comparative study of the high-pressure behaviours of the nuclear waste immobilisation materials zirconolite-2M, −4M, –3O, and −3T. The materials are studied under high-pressure conditions using synchrotron powder X-ray diffraction. For zirconolite-2M we also performed density-functional theory calculations. A new triclinic crystal structure (space group P1¯), instead of the previously assigned monoclinic structure (space group C2/c) is proposed for zirconolite-2M. We named the triclinic structure as zirconolite-2TR. We also found that zirconolite-2TR undergoes a phase transition at 14.7 GPa to a monoclinic structure described by space group C2/c, which is different than the high-pressure structure previously proposed in the literature. These results are discussed in comparison with previous studies on zirconolite-2M and the related compound calzirtite. For the other three zirconolite structures (4M, 3O, and 3T) this is the first high-pressure study, and we find no evidence for pressure induced phase transitions in any of them. The linear compressibility of the studied compounds, as well as a room-temperature pressure–volume equation of state, are also presented and discussed.

Size-Dependent High-Pressure Behavior of Pure and Eu3+-Doped Y2O3 Nanoparticles: Insights from Experimental and Theoretical Investigations.

We report a joint high-pressure experimental and theoretical study of the structural, vibrational, and photoluminescent properties of pure and Eu3+-doped cubic Y2O3 nanoparticles with two very different average particle sizes. We compare the results of synchrotron X-ray diffraction, Raman scattering, and photoluminescence measurements in nanoparticles with ab initio density-functional simulations in bulk material with the aim to understand the influence of the average particle size on the properties of pure and doped Y2O3 nanoparticles under compression. We observe that the high-pressure phase behavior of Y2O3 nanoparticles depends on the average particle size, but in a different way to that previously reported. Nanoparticles with an average particle size of ~37 nm show the same pressure-induced phase transition sequence on upstroke and downstroke as the bulk sample; however, nanoparticles with an average particle size of ~6 nm undergo an irreversible pressure-induced amorphization above 16 GPa that is completed above 24 GPa. On downstroke, 6 nm nanoparticles likely consist of an amorphous phase.

Structural, mechanical and electronic properties and phase transitions in superhard BC1-xNx: A first-principles study

First-principles investigations of the stability, mechanical properties, electronic and phonon structures, as well as molecular dynamics simulations of temperature- and pressure-induced phase transitions in boron carbonitrides, BC1-xNx, for x = 1.0 (C0), 0.75 (C1), 0.5 (C2), 0.25 (C3) and 0.0 (C4), were carried out. The plausible mechanisms of the phase transitions in BNs were proposed and the transformation paths were established for the h → w, r → c, c → r and w → h’ transitions, where h’ was the new hP4-187 phase (space group P-6m2, #187). The non-layered C0–C3 compounds transformed into the layered ones at 2000–3000 K. The new BC1-xNx structures are brittle materials and exhibit the best combination of hardness (23.1–60.8 GPa) and fracture toughness (4.03–5.23 MPa m1/2). The C1–C4 structures are metallic, except for three compounds: C1-oP8-25 and C4-tP8-136 are semi-metals, and C4-mP8-10 is a semiconductor with a very narrow bandgap of 0.2 eV.

The role of local non-tetragonal polar displacements in the temperature- and pressure-induced phase transitions in PbTiO3-BiMeO3 ferroelectrics

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Pressure-induced magnetic phase and structural transition in SmSb2

Abstract Motivated by the recent discovery of unconventional superconductivity around a magnetic quantum critical point in pressurized CeSb2, here we present a high-pressure study of an isostructural antiferromagnetic (AFM) SmSb2 through electrical transport and synchrotron x-ray diffraction measurements. At P C ~2.5 GPa, we found a pressure-induced magnetic phase transition accompanied by a Cmca→P4/nmm structural phase transition. In the pristine AFM phase below P C, the AFM transition temperature of SmSb2 is insensitive to pressure; in the emergent magnetic phase above P C, however, the magnetic critical temperature increases rapidly with increasing pressure. In addition, at ambient pressure, the magnetoresistivity (MR) of SmSb2 increases suddenly upon cooling below the AFM transition temperature and presents linear nonsaturating behavior under high field at 2 K. With increasing pressure above P C, the MR behavior remains similar to that observed at ambient pressure, both in terms of temperature- and field-dependent MR. This leads us to argue an AFM-like state for SmSb2 above P C. Within the investigated pressure of up to 45.3 GPa and the temperature of down to1.8 K, we found no signature of superconductivity in SmSb2.

Pressure-induced phase transition and metallization in zirconium disulfide under different hydrostatic environments up to 25.3 GPa

The pressurized behaviours of structure, vibration and electrical transport in zirconium disulfide have been systematically investigated in a diamond anvil cell (DAC) under different hydrostatic environments up to 25.3 GPa utilizing in-situ Raman spectroscopy, electrical conductivity measurement, high-resolution transmission electron microscopy (HRTEM) and first-principles theoretical calculations. Upon compression, our experimental results showed that ZrS2 underwent a phase transition accompanied by a semiconductor-to-metal transformation at 15.4 GPa under non-hydrostatic condition. Under hydrostatic condition, the corresponding phase transition occurred at a higher pressure of 17.5 GPa, indicating that the high-pressure phase transition is sensitive to the hydrostaticity in the sample chamber of DAC. Upon decompression, some absolutely new Raman peaks emerged at the pressures below 4.8 GPa and 2.9 GPa under non-hydrostatic and hydrostatic environments, respectively, which revealed an irreversible phase transition in ZrS2. Furthermore, our observations from selected-area electron diffraction patterns confirmed the irreversibility of the high-pressure phase transformation.