High-pressure Synchrotron X-ray Diffraction Research Articles

A theoretical investigation on the structural stability, superconductivity, and optical and thermodynamic properties of Ir2P under pressure.

The potential applications of Ir2P are promising due to its desirable hardness, but its fundamental properties are still not fully understood. In this study, we present a systematic investigation of Ir2P's structural, electronic, superconducting, optical, and thermodynamic properties of Ir2P under pressure. Our calculations show that Ir2P has a Fm3̄m structure at ambient pressure, which matches well with experimental data obtained from high-pressure synchrotron X-ray diffraction. As pressure increases, a transition from the Fm3̄m to the I4/mmm phase occurs at 103.4 GPa. The electronic structure and electron-phonon coupling reveal that the Fm3̄m and I4/mmm phases of Ir2P are superconducting materials with superconducting transition temperatures of 2.51 and 0.89 K at 0 and 200 GPa, respectively. The optical properties of Ir2P indicate that it has optical conductivity in the infrared, visible, and ultraviolet regions. Additionally, we observed that the reflectivity R(ω) of Ir2P is higher than 76% in the 25-35 eV energy range at different pressures, which suggests that it could be used as a reflective coating. We also explored the finite-temperature thermodynamic properties of Ir2P, including the Debye temperature, the first and second pressure derivatives of the isothermal bulk modulus, and the thermal expansion coefficient up to 2000 K using the quasi-harmonic Debye model. Our findings offer valuable insights for engineers to design better devices.

Anisotropic thermo-mechanical response of layered hexagonal boron nitride and black phosphorus: application as a simultaneous pressure and temperature sensor.

Hexagonal boron nitride (hBN) and black phosphorus (bP) are crystalline materials that can be seen as ordered stackings of two-dimensional layers, which lead to outstanding anisotropic physical properties. Knowledge of the thermal equations of state of hBN and bP is of great interest in the field of 2D materials for a better understanding of their anisotropic thermo-mechanical properties and exfoliation mechanism towards the preparation of important single-layer materials like hexagonal boron nitride nanosheets and phosphorene. Despite several theoretical and experimental studies, important uncertainties remain in the determination of the thermoelastic parameters of hBN and bP. Here, we report accurate thermal expansion and compressibility measurements along the individual crystallographic axes, using in situ high-temperature and high-pressure high-resolution synchrotron X-ray diffraction. In particular, we have quantitatively determined the subtle variations of the in-plane and volumetric thermal expansion coefficients and compressibility parameters by subjecting these materials to hydrostatic conditions and by collecting a large number of data points in small pressure and temperature increments. In addition, based on the anisotropic behavior of bP, we propose the use of this material as a sensor for the simultaneous determination of pressure and temperature in the range of 0-5 GPa and 298-1700 K, respectively.

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.

High-pressure structural phase transition on Bi14MoO24

In situ high-pressure powder synchrotron X-ray diffraction studies on tetragonal Bi14MoO24 have been carried out up to 11.5 GPa at room temperature. A tetragonal (I4/m) to monoclinic (C2/m) structural phase transition has been identified around 5 GPa and possible evidence for a second phase transition is observed at the highest pressure of this study. Both phase transitions are reversible upon decompression. The evolution of the lattice parameters, axial ratio, and volume under pressure have been determined for both the low pressure tetragonal and high-pressure monoclinic phases. A volume collapse of 2.7% observed at the tetragonal to monoclinic phase transition indicates it to be of first-order character. The phase transition involves a shear deformation perpendicular to the b-axis and a displacement of the Mo atoms along the b-axis. The details of the mechanism of the tetragonal-monoclinic transition are discussed. The bulk modulus of the low-pressure tetragonal and high-pressure monoclinic phases have been estimated to be 67(7) GPa and 64(3) GPa, respectively. The linear compressibilities of both phases show an anisotropic response to pressure. The obtained results are compared with the high-pressure behavior of its isomorph counterpart Bi14CrO24 and with high-temperature behavior on Bi14MoO24.

Coexistence of zigzag antiferromagnetic order and superconductivity in compressed NiPSe3

NiPSe3 is regarded as a bandwidth-controlled Mott insulator, distinct from the widely studied Mott insulating magnetic graphene MPSe3 (M = Mn and Fe) family. By employing high-pressure synchrotron X-ray diffraction, we observe two structural transitions as a function of pressure. With the help of first-principles calculations, we discover the antiferromagnetic (AFM) moment directions of NiPSe3 switch from out-of-plane to in-plane and the honeycomb layers slide relative to each other at the first structural transition. The in-plane AFM order persists until the second structural transition, whereupon the two-dimensional (2D) structure assumes a more three-dimensional (3D) character. A bandwidth-controlled Mott insulator-metal transition (IMT) occurs between the two structural transitions at Pc ~ 8.0 GPa, concomitant with the emergence of superconductivity with Tc ~ 4.8 K. The superconductivity in NiPSe3 emerging in the 2D monoclinic phase coexists with the in-plane AFM order and continues into the 3D trigonal phase. Our electronic structure calculations reveal that the IMT and superconductivity in NiPSe3 are both related to the enhanced Se2− 4p and Ni2+3d electronic hybridizations under pressure. From these results, we construct a temperature-pressure electronic phase diagram of NiPSe3, revealing interesting relationships between magnetism and superconductivity.

Pressure effect on the electrical properties and pressure-induced phase transitions in a three-dimensional Dirac semimetal BaAgBi

High pressure is an effective and clean method for tuning lattice structures and electronic states. In this study, we report on the crystal growth and experimental study of the pressure effect on the three-dimensional Dirac semimetal BaAgBi. Within the pressure range of 51.8 GPa studied in this work, BaAgBi remained metallic and no superconductivity was observed down to 1.6 K. The resistance is primarily governed by the electron-phonon and s-d electron-electron scattering. High-pressure synchrotron X-ray diffraction experiments indicated the presence of two high-pressure phases below 50 GPa, and the crystal structures were proposed to be Pnma and Pca21, respectively. By refining the high-pressure X-ray data, we plotted the pressure dependence of unit cell volumes and obtained the bulk modulus for all three phases.

Pressure-induced nonmonotonic cross-over of steady relaxation dynamics in a metallic glass

Relaxation dynamics, as a key to understand glass formation and glassy properties, remains an elusive and challenging issue in condensed matter physics. In this work, insitu high-pressure synchrotron high-energy X-ray photon correlation spectroscopy has been developed to probe the atomic-scale relaxation dynamics of a cerium-based metallic glass during compression. Although the sample density continuously increases, the collective atomic motion initially slows down as generally expected and then counterintuitively accelerates with further compression (density increase), showing an unusual nonmonotonic pressure-induced steady relaxation dynamics cross-over at ~3 GPa. Furthermore, by combining insitu high-pressure synchrotron X-ray diffraction, the relaxation dynamics anomaly is evidenced to closely correlate with the dramatic changes in local atomic structures during compression, rather than monotonically scaling with either sample density or overall stress level. These findings could provide insight into relaxation dynamics and their relationship with local atomic structures of glasses.

High-Pressure Experimental and DFT Structural Studies of Aurichalcite Mineral

We report on high-pressure angle-dispersive synchrotron X-ray diffraction data of a natural Zn3.78(2)Cu1.22(2)(CO3)2(OH)6 aurichalcite mineral up to 7.6 GPa and ab initio total energy calculations of the aurichalcite structure with three different Zn-Cu stoichiometries (Zn:Cu ratios = 10:0, 8:2 and 6:4). A monoclinic-to-triclinic displacive second-order phase transition was found experimentally at 3 GPa. The experimental bulk modulus of the initial P21/m aurichalcite is B0 = 66(2) GPa, with a first-pressure derivative of B0′ = 9(2). A comparison with other basic copper and zinc carbonates shows that this B0 value is considerably larger than those of malachite and azurite. This relative incompressibility occurs despite the fact that aurichalcite features a layered structure due to the number of directed hydrogen bonds between carbonate groups and the cation-centered oxygen polyhedra forming complex sheets. The existence of different bond types and polyhedral compressibilities entails a certain anisotropic compression, with axial compressibilities κa0 = 3.79(5)·10−3 GPa−1, κb0 = 5.44(9)·10−3 GPa−1 and κc0 = 4.61(9)·10−3 GPa−1. Additional density-functional theory calculations on the C2/m hydrozincite-type structure with different Zn:Cu compositional ratios shows that the aurichalcite structure is energetically more stable than the hydrozincite one for compositions of Zn:Cu = 10:0, 8:2 and 6:4 at room pressure. The pure Zn aurichalcite phase, however, was predicted to transform into hydrozincite at 18 GPa, which suggests that the experimentally observed hydrozincite structure is a metastable phase.

Nanolamellar phase transition in an additively manufactured eutectic high-entropy alloy under high pressures

Much is unknown about how phase transitions link to micro-/nano-structures in high-entropy systems, especially under extreme pressure and temperature conditions. This work studies the evolution of dual-phase nanolamellar eutectic high-entropy alloy phases of AlCoCrFeNi2.1 generated by laser powder-bed fusion (L-PBF) for pressures up to 42 GPa. We compare quasi-hydrostatic high pressure synchrotron x-ray diffraction studies on L-PBF printed cylindrical samples up to 5.5 GPa (large-volume Paris–Edinburgh cell) to those carried out on an L-PBF printed foil in a diamond anvil cell where the pressure reached 42 GPa. Our results show that the initially alternating face-centered cubic (FCC) and body-centered cubic (BCC) nanolamellar structure of AlCoCrFeNi2.1 transformed into single-phase FCC nanolamellae under high pressure with BCC–FCC phase transformation completion at 21 ± 3 GPa. Our results indicate a diffusionless BCC–FCC transformation in this additively manufactured far-from-equilibrium microstructure and demonstrate that the FCC phase is stable up to very high pressures. The measured equation of state for the FCC phase of AlCoCrFeNi2.1 is presented up to 42 GPa and shows excellent agreement between the data obtained in large-volume press and diamond anvil cell experiments.

Evidence of pressure-induced multiple electronic topological transitions in BiSe

BiSe, an exciting member of homologous family (Bi2)m (Bi2Se3)n [where, m = 1; n = 2], has recently gained attention in thermoelectric research due to its intrinsically ultralow lattice thermal conductivity and promising n-type thermoelectric performance near room temperature. It is experimentally observed to be a weak topological insulator and possesses a fascinating crystal structure where Bi2 bilayer is sandwiched between two Bi2Se3 quintuple layers, thus the structure resembles natural van der Waals heterostructure (Bi2Se3–Bi2–Bi2Se3). Herein, we have studied the pressure induced electronic topological transition (ETT) in BiSe through high pressure (0–10 GPa) synchrotron X-ray diffraction, Raman spectroscopy and first-principles density functional theory (DFT). We have observed clear anomalies at ∼1 and ∼2.2 GPa in the pressure dependent lattice parameters (a, c, and c/a ratio), cell volume, Raman mode shift and line width data suggesting the presence of two ETTs which is further verified by electronic structures and Fermi surface calculations under pressure. The origin of these ETTs is associated with the two different vibrational modes arising from Bi2 bilayer and Bi2Se3 quintuple layers of BiSe, respectively.

Determination of P–V equation of state of a natural clinoptilolite using high-pressure powder synchrotron X-ray diffraction

Determination of P–V equation of state of a natural clinoptilolite using high-pressure powder synchrotron X-ray diffraction

Superconductivity in Layered van der Waals Hydrogenated Germanene at High Pressure.

The emergence of superconductivity in two-dimensional (2D) materials has attracted tremendous research efforts because the origins and mechanisms behind the unexpected and fascinating superconducting phenomena remain unclear. In particular, the superconductivity can survive in 2D systems even with weakened disorder and broken spatial inversion symmetry. Here, structural and superconducting transitions of 2D van der Waals (vdW) hydrogenated germanene (GeH) are observed under compression and decompression processes. GeH possesses a superconducting transition with a critical temperature (Tc) of 5.41 K at 8.39 GPa. A crystalline to amorphous transition occurs at 16.80 GPa, while superconductivity remains. An abnormal increase of Tc up to 6.11 K was observed during the decompression process, while the GeH remained in the 2D amorphous phase. A combination study of in situ high-pressure synchrotron X-ray diffraction, in situ high-pressure Raman spectroscopy, transition electron microscopy, and density functional theory simulations suggests that the superconductivity in 2D vdW GeH is attributed to the increased density of states at the Fermi level as well as the enhanced electron-phonon coupling effect under high pressure even in the form of an amorphous phase. The unique pressure-induced phase transition of GeH from 2D crystalline to 2D amorphous metal hydride provides a promising platform to study the mechanisms of amorphous hydride superconductivity.

Variation of the critical temperature with the lattice parameter in K3C60

Alkali-doped fullerides are a fascinating system exhibiting the convergence of s-wave superconductivity and Mott physics. A direct relationship between the critical temperature Tc and lattice constant established by applying physical or chemical pressure in these compounds is generally believed to be the foundation for the identification of the microscopic electron pairing(s). Here the evolution of Tc with lattice compression for the first fulleride K3C60 is systematically studied via the high-pressure electrical transport and synchrotron x-ray diffraction measurements on the same well-characterized sample. The combination of the theoretically calculated density of states at the Fermi level, the electron-phonon coupling and mean phonon-frequency determined from high-pressure Raman spectra yields the Coulomb pseudopotential ranging from 0.15 to 0.32 with increasing pressure in terms of the McMillan formula. This indicates that the conventional phonon-mediated mechanism cannot account for the high-pressure evolution of Tc solely. However, the obtained pressure derivative of Tc and bulk modulus are used to reproduce well the experimentally observed isotope exponent in this superconductor within the theoretical framework of the non-phononic theory. These results and findings together demonstrate the important role of the study of the lattice effect on Tc played in determining the mechanisms of superconductivity in fullerides.

Structural stability of orthorhombic DyScO3 under extreme conditions of pressure and temperature

In the present work, the effect of elevated pressure and lowered temperature on the structural and vibrational stability of dysprosium scandate (${\mathrm{DyScO}}_{3}$) is studied via high-pressure synchrotron x-ray diffraction (HPXRD) and high-pressure (HP) and low-temperature Raman spectroscopy. A solid-state reaction route is employed to synthesize the material with a crystallite size of 92 nm, which at ambient conditions exhibits an orthorhombic phase with the space group $Pbnm$ (62). HPXRD results reveal excellent phase stability of the material, with the ratio of the polyhedral volumes and the compressibility for the ${\mathrm{DyO}}_{12}$ and ${\mathrm{ScO}}_{6}$ polyhedra to be around 4.26 and 1 for the entire applied pressure range of up to 40 GPa. Interestingly, the combination of HPXRD and HP Raman measurements signals a change in the preferred orientations in the crystalline structure with the increased pressure, while keeping the structure stable. The bulk modulus of the material is estimated to be 189.4 GPa from the HPXRD data and is further used to estimate the mode Gr\"uneisen parameter (\ensuremath{\gamma}) for various Raman modes. The behavior of phonon frequency with varying temperature is explained by considering the anharmonic effects, i.e., lattice expansion and perturbation in the Hamiltonian, with an increase in temperature. Furthermore, the implicit and explicit anharmonicity contributions were calculated to elucidate the phonon decay mechanisms. Our results offer valuable insights relating to the behavior of this intriguing class of materials under extreme conditions and lays the foundation for further exploration.

Mechanical properties of hexagonal silicon

Hexagonal silicon (Si-IV) has recently attracted considerable research interest due to its extraordinary optical properties and possibility to convert into a direct semiconductor under strain with great potential for applications. However, the mechanical properties of Si-IV, which are critical for its applications, have not been experimentally studied yet. In this study, combining nanoindentation and in situ high-pressure synchrotron X-ray diffraction, we thoroughly investigated the mechanical properties of Si-IV. The results suggest that the elastic moduli and hardness of Si-IV are close to those of the common diamond cubic silicon. The similar mechanical properties of Si-IV and diamond cubic silicon are beneficial for integrating Si-IV into conventional Si-based devices using similar industrial processing and for its photovoltaic and optoelectronic applications.

Accurate crystal structure of ice VI from X-ray diffraction with Hirshfeld atom refinement.

Water is an essential chemical compound for living organisms, and twenty of its different crystal solid forms (ices) are known. Still, there are many fundamental problems with these structures such as establishing the correct positions and thermal motions of hydrogen atoms. The list of ice structures is not yet complete as DFT calculations have suggested the existence of additional and - to date - unknown phases. In many ice structures, neither neutron diffraction nor DFT calculations nor X-ray diffraction methods can easily solve the problem of hydrogen atom disorder or accurately determine their anisotropic displacement parameters (ADPs). Here, accurate crystal structures of H2O, D2O and mixed (50%H2O/50%D2O) ice VI obtained by Hirshfeld atom refinement (HAR) of high-pressure single-crystal synchrotron and laboratory X-ray diffraction data are presented. It was possible to obtain O-H/D bond lengths and ADPs for disordered hydrogen atoms which are in good agreement with the corresponding single-crystal neutron diffraction data. These results show that HAR combined with X-ray diffraction can compete with neutron diffraction in detailed studies of polymorphic forms of ice and crystals of other hydrogen-rich compounds. As neutron diffraction is relatively expensive, requires larger crystals which can be difficult to obtain and access to neutron facilities is restricted, cheaper and more accessible X-ray measurements combined with HAR can facilitate the verification of the existing ice polymorphs and the quest for new ones.

Pressure-induced reemergence of superconductivity in BaIr2Ge7 and Ba3Ir4Ge16 with cage structures

Clathrate-like or caged compounds have attracted great interest owing to their structural flexibility, as well as their fertile physical properties. Here, we report the pressure-induced reemergence of superconductivity in BaIr2Ge7 and Ba3Ir4Ge16, two new caged superconductors with two-dimensional building blocks of cage structures. After suppression of the ambient-pressure superconducting (SC-I) states, new superconducting (SC-II) states emerge unexpectedly, with Tc increased to a maximum of 4.4 and 4.0 K for BaIr2Ge7 and Ba3Ir4Ge16, respectively. Combined with high-pressure synchrotron x-ray diffraction and Raman measurements, we propose that the reemergence of superconductivity in these caged superconductors can be ascribed to a pressure-induced phonon softening linked to cage shrinkage.

Reversible linear-compression behavior of free volume in a metallic glass

Free volume is one of the key structural concepts widely used to describe various glass phenomena. However, free volume is challenging to be rigorously defined in glass structures and directly determined by experiments. Here, we employed metallic glass as a simple glass model system and studied the structural evolution of an as-spun (hyperquenched) and another thermally annealed metallic glass with different amounts of free volume by in situ high-pressure synchrotron x-ray diffraction. Therefore, the effect of free volume on the compression behavior of metallic glasses can be clarified by comparing the two samples at identical experimental conditions. We find that a higher amount of free volume causes both lower density and bulk modulus as expected at ambient conditions. Surprisingly, during compression, the decrease of free volume has a constant rate up to $\ensuremath{\sim}30\phantom{\rule{0.16em}{0ex}}\mathrm{GPa}$ and appears to be mostly reversible upon decompression without obvious permanent densification after pressure release. These results suggest an elastic process in metallic glasses under pressure. Implications of these results for the structural models based on the free-volume concept are discussed. The typically assumed glass structural model with isolated domains of ``liquidlike'' (free-volume rich) region embedded in a solidlike (free-volume poor) matrix seems unlikely. Instead, a more ``homogeneous'' model over a wide range of length scales such as a nested fractal network of liquid- and solidlike regions seems more consistent with the experimental observation.

Preparation of Al2O3–Cr2O3 Solid Solutions as Buoyancy Markers and Their High Pressure Synchrotron X-ray Diffraction Analysis

Preparation of Al2O3–Cr2O3 Solid Solutions as Buoyancy Markers and Their High Pressure Synchrotron X-ray Diffraction Analysis

Pressure-induced phase transition and increase of oxygen-iodine coordination in magnesium iodate

The structural and vibrational behavior of $\mathrm{Mg}{({\mathrm{IO}}_{3})}_{2}$ under compression has been investigated via a combination of high-pressure (HP) synchrotron x-ray diffraction (XRD), Raman scattering, and infrared spectroscopy experiments as well as first-principles ab initio calculations. In this paper, we reveal that $\mathrm{Mg}{({\mathrm{IO}}_{3})}_{2}$ undergoes a pressure-induced phase transition between 7.5 and 9.7 GPa at ambient temperature from a monoclinic (space group $P{2}_{1}$) to a trigonal (space group P3) structure. $\mathrm{Mg}{({\mathrm{IO}}_{3})}_{2}$ also exhibits the gradual formation of additional bonds between iodine and oxygen atoms in neighboring ${\mathrm{IO}}_{3}^{\ensuremath{-}}$ units with increasing pressure, thereby increasing the oxygen-iodine coordination from 3 to 6. The bond formation under compression is a consequence of the existence of lone electron pairs on the iodine cation. To accommodate the additional bonds, the I--O bonds within the original ${[{\mathrm{IO}}_{3}]}^{\text{--}}$ trigonal pyramids increase in length under increasing compression. The appearance of additional Raman modes at 7.7 GPa and infrared modes at 9.6 GPa supports the phase transition observed in XRD experiments. Interestingly, the lengthening of I--O bonds causes a softening of several Raman modes under compression. We provide the crystal structure of the HP phase, the pressure-volume equations of state for both low- and HP phases, and the symmetry assignment of the Raman- and infrared-active modes of both phases.