Pressure-temperature Phase Diagram Research Articles

Pressure-induced evolution of structures and phase transition of technetium diboride

Using the particle swarm optimization algorithm, we conducted an extensive search for the high-pressure stable structure of technetium diboride (TcB2) within the pressure range of 0–400 GPa. At zero pressure, the P63/mmc (hP6-TcB2) structure is considered the ground state configuration. As the pressure increases, a structural transition from hP6-TcB2 to P6/mmm (hP3-TcB2) occurs at approximately 174.9 GPa. We discuss the bonding between the two distinct phases and analyze the contribution of different atomic bonds to maintaining their structural stability. Meanwhile, the temperature–pressure phase diagram of TcB2 was successfully determined for the first time through the quasi-harmonic approximation method. It is predicted that the transition pressure from hP6-TcB2 to hP3-TcB2 can be reduced to about 164 GPa at a room temperature of 300 K. These results provide valuable insights into the behavior of TcB2 under different temperature and pressure conditions and open up new possibilities for exploring its potential applications in a variety of environments.

Thermoresponsive Polymers under Pressure with a Focus on Poly(N-isopropylacrylamide) (PNIPAM).

Pressure is a key variable in the phase behavior of responsive polymers, both for applications and from a fundamental point of view. In this feature article, we review recent developments, particularly applications of neutron techniques such as small-angle neutron scattering (SANS) and quasi-elastic neutron scattering (QENS), across the temperature-pressure phase diagram. These are complemented by kinetic SANS experiments following pressure jumps. In the prototype system poly(N-isopropylacrylamide) (PNIPAM), QENS revealed the pressure-dependent characteristics of hydration water around the lower critical solution temperature transition. The size, water content, and inner structure of the mesoglobules formed in the two-phase region depend strongly on pressure, as shown by SANS. Beside these changes at the phase transition, the mesoglobule formation at low pressure is determined by kinetic factors, namely the formation of a polymer-rich, rigid shell, which hampers further growth by coalescence. At high pressure, in contrast, the growth proceeds by diffusion-limited coalescence without any kinetic hindrance. The disintegration of the mesoglobules evolves either via chain release from their surface or via swelling, depending on the osmotic pressure of the water. Moreover, we report on the profound influence of pressure on the cononsolvency effect. In the temperature-pressure frame, the one-phase region is hugely expanded upon the addition of the cosolvent methanol. SANS experiments unveil the enthalpic and entropic contributions to the effective Flory-Huggins interaction parameter between the segments and the solvent mixture. QENS experiments demonstrate an increase in polymer associated water with pressure, whereas methanol is released. Correspondingly, the solvent phase becomes enriched in methanol, providing a mechanism for the breakdown of cononsolvency at a high pressure. Finally, we outline future opportunities for high-pressure studies of thermoresponsive polymers, with a focus on neutron methods.

Pressure-induced linear enhancement of the superconducting transition in Nd0.8Sr0.2NiO2 thin films

We report the pressure (P) effect on the superconducting transition temperature T c and the upper critical field μ 0 H c2 of infinite-layer Nd0.8Sr0.2NiO2 thin films by measuring the electrical transport properties under various hydrostatic pressures to 4.6 GPa. At ambient pressure, it shows the clear superconducting transition with T c ∼ 10 K. Based on the evolution of resistance R(T), we found that the T c is monotonically enhanced to ∼14 K upon increasing pressure to 2.9 GPa. The constructed temperature–pressure phase diagram indicates that the calculated slope dT c/dP is about 1.14 K GPa−1 and the superconducting T c shows no signatures of saturation with pressure. It thus gives the possibility to further enhance T c by employing higher pressures or heterostructure engineering. In addition, the normalized slope of upper critical field μ 0 H c2(0) implies that the electron correlations are gradually decreasing with pressure, which exhibits an opposite evolution with superconducting T c. Our work further confirms the positive pressure effects in nickelate superconductors and gives more insight to further enhance its superconducting transition temperature.

Competitive nucleation and growth control of a- and c-axis YBCO films by metal organic deposition

This paper utilizes the TFA-MOD (Trifluoroacetate Metal-Organic Decomposition) method to prepare YB2C3O7-δ (YBCO) superconducting films on a LaMnO3 metal substrate. Using a self-made process curve, we investigate the nucleation and growth orientation of crystals at various temperatures under specific oxygen partial pressures (PO2). We successfully obtain an oxygen partial pressure-temperature phase diagram at a fixed time. This diagram provides critical insight into the trends that guide our regulation of parameters to ultimately achieve a relatively pure a-axis oriented YBCO film. Temperature and nucleation rate are important parameters that influence crystal nucleation orientation. The key conditions for producing a-axis-oriented YBCO films include low temperature, high Δμ, and extended crystallization time.

High-temperature and high-pressure thermal property measurements of SiO2 crystals.

The investigation of materials' behavior under high-temperature and high-pressure conditions, such as the correlation with structural characteristics and thermal properties, holds significant importance. However, the challenges associated with the experimental implementation have, to a certain extent, constrained such research endeavors. We utilized the ultrafast laser based non-contact thermal measurement method combined with an externally heated moissanite-anvil-cell to characterize the thermal conductivity of [10-10] oriented SiO2 crystals under high temperature (300-830K) and high pressure (0-15GPa) conditions. We investigated the impact of extreme conditions on the microstructure from both Raman spectroscopy and thermal perspectives. The presence of kinetic hindrances associated with the transformation of α-quartz to coesite and stishovite was identified and confirmed. It expands the comprehension and application of the SiO2 pressure-temperature phase diagram in this range and provides insights into the intricate relationship between extreme environments and material structure formation through the analysis of thermal characteristics.

First-principles lattice dynamics and thermodynamic properties of α-, θ-, κ- and γ-Al2O3 and solid state temperature-pressure phase diagram

γ-Al2O3 is a commonly observed high temperature alumina phase during Al-based alloy oxidation. Due to the partially ordered, defective nature of the spinel structure arising from the partial occupancy in the Al sites, first-principles prediction of the thermodynamic properties of γ-Al2O3 has been challenging. In this work, employing the first-principles quasiharmonic approach, we obtain the finite temperature thermodynamic properties of γ-Al2O3, including entropy, chemical potential, heat capacity, thermal expansion coefficient, and elastic constants and the results are compared with those calculated for the other three alumina phases, i.e., α-Al2O3, θ-Al2O3, and κ-Al2O3. The calculated lattice constants and the predicted relative phase stability under 0 K and 0 GPa, α>κ>θ>γ, are consistent with experimental values and existing calculations, respectively. Based on the results, we constructed the temperature-pressure phase diagram covering the four Al2O3 phases (α, κ, θ, γ), which could provide for experimentally synthesizing the different alumina phases.

High pressure–temperature phase diagram of ammonia hemihydrate

High pressure–temperature phase diagram of ammonia hemihydrate

Interplay of Kinetic Limitations and Disintegration: Selective Growth of Hexagonal Boron Nitride and Borophene Monolayers on Metal Substrates.

The CVD growth of bielemental 2D-materials by using molecular precursors involves complex formation kinetics taking place at the surface and sometimes also subsurface regions of the substrate. Competing microscopic processes fundamentally limit the parameter space for optimal growth of the desired material. Kinetic limitations for diffusion and nucleation cause a high density of small domains and grain boundaries. These are usually overcome by increasing the growth temperature and decreasing the growth rate. In contrast, the nature of molecular precursors with limited thermal stability can result in dissociation and preferential desorption, leading to an undesired or ill-defined composition of the 2D-material. Here we demonstrate these constraints in a combined low-energy electron diffraction and low-energy electron microscopy study by examining the selective formation of single-layer hexagonal boron nitride (hBN) and borophene on Ir(111) using a borazine precursor. We derive a temperature-pressure phase diagram and apply classical nucleation theory to describe our results. By considering the competing processes, we find an optimum growth temperature for hBN of 950 °C. At lower temperatures, the hBN island density is increased, while at higher temperatures the precursor disintegrates and borophene is formed. Our results introduce an additional aspect that must be considered in any high-temperature growth of bielemental 2D-materials from single molecular precursors.

Coupled magnetic and structural transition in topological antiferromagnet EuAgAs under high pressure

Recently, EuAgAs and its derivatives have emerged as a promising platform for studying the interplay of transports, magnetism and topology. Herein, we report construction of a temperature-pressure phase diagram for antiferromagnetic Dirac semimetal EuAgAs, through electrical transport, synchrotron x-ray diffraction and Raman spectroscopy measurements in diamond anvil cells at high pressures up to 48.6 GPa. At Pc1∼3–5 GPa, we found a pressure-induced magnetic phase transition with accompanying a structural P63/mmc→Pnma transition. In the pristine antiferromagnetic phase, negative colossal magnetoresistance is observed mainly below the Néel temperature TN along with a field-induced metamagnetic transition; in the emergent magnetic phase, however, it is evident both above and below the magnetic critical temperature TC yet with no field-induced metamagnetic transition. These distinct features lead us to argue a ferromagnetic-like state for EuAgAs above Pc1, which is further supported by observation of a T5/3 temperature dependence of low-temperature resistance, a characteristic of marginal Fermi-liquid state expected to exist close to a ferromagnetic instability by spin fluctuations in metallic ferromagnets. At Pc2∼20 GPa, a possible phase transition of electronic origin may take place, which is revealed jointly by change of a T5/3→T5/2 temperature dependence of low-temperature resistance and change in slope of linear-in-T resistance at high temperatures.

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.

Exploring the configuration space of elemental carbon with empirical and machine learned interatomic potentials

We demonstrate how the many-body potential energy landscape of carbon can be explored with the nested sampling algorithm, allowing for the calculation of its pressure-temperature phase diagram. We compare four interatomic potential models: Tersoff, EDIP, GAP-20 and its recently updated version, GAP-20U. Our evaluation is focused on their macroscopic properties, melting transitions, and identifying thermodynamically stable solid structures up to at least 100 GPa. The phase diagrams of the GAP models show good agreement with experimental results. However, we find that the models’ description of graphite includes thermodynamically stable phases with incorrect layer spacing. By adding a suitable selection of structures to the database and re-training the potential, we have derived an improved model — GAP-20U+gr — that suppresses erroneous local minima in the graphitic energy landscape. At extreme high pressure nested sampling identifies two novel stable structures in the GAP-20 model, however, the stability of these is not confirmed by electronic structure calculations, highlighting routes to further extend the applicability of the GAP models.

An unexpected high-pressure stability domain for a lower density polymorph of benzophenone

For over a century, it was thought that the crystalline polymorph II of benzophenone does not possess a stable domain in the pressure–temperature phase diagram. With a combination of new experimental results and literature data, this case of crystalline dimorphism has finally been solved and it is shown that form II possesses a stable domain at high pressure and high temperature, even though its density is lower than that of form I, the stable form under ordinary pressure and temperature conditions. The phase diagram of benzophenone is a clear demonstration of the fact that to understand the phase behaviour of a chemical substance both the exchange of heat (due to the change in intermolecular interactions) and work (due to the change of volume at a given pressure) need to be taken into account.

Temperature-pressure phase diagram of confined monolayer water/ice at first-principles accuracy with a machine-learning force field

Understanding the phase behaviour of nanoconfined water films is of fundamental importance in broad fields of science and engineering. However, the phase behaviour of the thinnest water film – monolayer water – is still incompletely known. Here, we developed a machine-learning force field (MLFF) at first-principles accuracy to determine the phase diagram of monolayer water/ice in nanoconfinement with hydrophobic walls. We observed the spontaneous formation of two previously unreported high-density ices, namely, zigzag quasi-bilayer ice (ZZ-qBI) and branched-zigzag quasi-bilayer ice (bZZ-qBI). Unlike conventional bilayer ices, few inter-layer hydrogen bonds were observed in both quasi-bilayer ices. Notably, the bZZ-qBI entails a unique hydrogen-bonding network that consists of two distinctive types of hydrogen bonds. Moreover, we identified, for the first time, the stable region for the lowest-density 4cdot {8}^{2} monolayer ice (LD-48MI) at negative pressures (<−0.3 GPa). Overall, the MLFF enables large-scale first-principle-level molecular dynamics (MD) simulations of the spontaneous transition from the liquid water to a plethora of monolayer ices, including hexagonal, pentagonal, square, zigzag (ZZMI), and hexatic monolayer ices. These findings will enrich our understanding of the phase behaviour of the nanoconfined water/ices and provide a guide for future experimental realization of the 2D ices.

A trust-region-based phase envelope construction algorithm

Pressure-temperature (PT) and pressure-composition (Px) phase diagrams play an important role in various chemical and petroleum engineering applications. Lots of algorithms based on the Newton-Raphson method have been proposed to numerically construct PT/Px phase envelopes. No attempt is made to improve the computational efficiency of such Newton-Raphson solution method. This work develops a new trust-region-based algorithm to replace the Newton-Raphson method to provide more robust and efficient phase envelope construction calculations. We first convert the phase envelope construction problem into a minimization problem by defining a least-squares objective function. We then apply the trust-region optimization method with an exact subproblem solver to minimize the objective function. We follow the general strategy proposed by Michelsen (1980) to develop the revised phase envelope construction algorithm. We demonstrate the good performance of the trust-region-based algorithm by comparing it with the conventional Newton's method. The computational results indicate that the new trust-region-based algorithm is more robust and cost-effective than the Newton-based algorithm.

Pressure effect of the charge density wave transition on Raman spectra and transport properties of 2H−NbSe2

Charge density wave (CDW) order is widely existing and fundamentally important in solid-state physics. However, several critical issues regarding the vibrational and electronic subsystems and their coupling still need to be better understood. Here, we tune the electrical transport and collective vibrational excitation, i.e., phonon and amplitude mode, by pressure in a prototype charge density wave material, $2H\text{\ensuremath{-}}{\mathrm{NbSe}}_{2}$. A complete pressure-temperature phase diagram is revisited. The anomaly in Hall and magnetoresistivity at CDW critical temperature, ${T}_{\mathrm{CDW}}$, was suppressed by the pressure. In the Raman spectroscopy measurements, the appearance of CDW amplitude mode is accompanied by the freezing of the two-phonon mode. The frequency of CDW amplitude mode under pressure follows modified mean-field theory with power-law scaling $(\ensuremath{\beta}=0.18)$. The renormalization of the Raman phonon across the CDW transition and the mean-field temperature dependence of CDW amplitude mode emphasized the importance of electron-phonon coupling in the formation of CDW state in $2H\text{\ensuremath{-}}{\mathrm{NbSe}}_{2}$. Our work clarifies the complex vibrational and electronic subsystems and sheds light on the mechanism of the charge density state in $2H\text{\ensuremath{-}}{\mathrm{NbSe}}_{2}$.

Data-driven prediction of complex crystal structures of dense lithium

Lithium (Li) is a prototypical simple metal at ambient conditions, but exhibits remarkable changes in structural and electronic properties under compression. There has been intense debate about the structure of dense Li, and recent experiments offered fresh evidence for yet undetermined crystalline phases near the enigmatic melting minimum region in the pressure-temperature phase diagram of Li. Here, we report on an extensive exploration of the energy landscape of Li using an advanced crystal structure search method combined with a machine-learning approach, which greatly expands the scale of structure search, leading to the prediction of four complex Li crystal structures containing up to 192 atoms in the unit cell that are energetically competitive with known Li structures. These findings provide a viable solution to the observed yet unidentified crystalline phases of Li, and showcase the predictive power of the global structure search method for discovering complex crystal structures in conjunction with accurate machine learning potentials.

The Phase Diagram of the API Benzocaine and Its Highly Persistent, Metastable Crystalline Polymorphs.

The availability of sufficient amounts of form I of benzocaine has led to the investigation of its phase relationships with the other two existing forms, II and III, using adiabatic calorimetry, powder X-ray diffraction, and high-pressure differential thermal analysis. The latter two forms were known to have an enantiotropic phase relationship in which form III is stable at low-temperatures and high-pressures, while form II is stable at room temperature with respect to form III. Using adiabatic calorimetry data, it can be concluded, that form I is the stable low-temperature, high-pressure form, which also happens to be the most stable form at room temperature; however, due to its persistence at room temperature, form II is still the most convenient polymorph to use in formulations. Form III presents a case of overall monotropy and does not possess any stability domain in the pressure-temperature phase diagram. Heat capacity data for benzocaine have been obtained by adiabatic calorimetry from 11 K to 369 K above its melting point, which can be used to compare to results from in silico crystal structure prediction.

Insulator–metal transition in CrSiTe3 triggered by structural distortion under pressure

van der Waals solids are well known to host remarkable phase diagrams with competing phases, unusual energy transfer processes, and elusive states of matter. Among this class of materials, chalcogenides have emerged as the most flexible and relevant platforms for unraveling charge–structure–function relationships. In order to explore the properties of complex chalcogenides under external stimuli, we measured the far infrared spectroscopic response of CrSiTe3 under extreme pressure–temperature conditions. Analysis of the 368 cm−1 Si–Te stretching mode and the manner in which it is screened by the closure of the indirect gap reveals that the insulator–metal transition takes place immediately after the structural phase transition—once the mixed phase aspect of the lattice distortion is resolved. At the same time, the two-phase region associated with the structural transition widens with decreasing temperature, and the slope of the insulator–metal transition under pressure is consistent with increasing entropy. These trends completely revise the character of the temperature–pressure phase diagram as well as the relationship between the structural and insulator–metal transitions, leading to a critical nexus of activity that may hide a quantum critical point and allow superconductivity to emerge.

A general-purpose machine learning Pt interatomic potential for an accurate description of bulk, surfaces, and nanoparticles.

A Gaussian approximation machine learning interatomic potential for platinum is presented. It has been trained on density-functional theory (DFT) data computed for bulk, surfaces, and nanostructured platinum, in particular nanoparticles. Across the range of tested properties, which include bulk elasticity, surface energetics, and nanoparticle stability, this potential shows excellent transferability and agreement with DFT, providing state-of-the-art accuracy at a low computational cost. We showcase the possibilities for modeling of Pt systems enabled by this potential with two examples: the pressure-temperature phase diagram of Pt calculated using nested sampling and a study of the spontaneous crystallization of a large Pt nanoparticle based on classical dynamics simulations over several nanoseconds.

Magnetic detection under high pressures using designed silicon vacancy centres in silicon carbide.

Pressure-induced magnetic phase transitions are attracting interest as a means to detect superconducting behaviour at high pressures in diamond anvil cells, but determining the local magnetic properties of samples is a challenge due to the small volumes of sample chambers. Optically detected magnetic resonance of nitrogen vacancy centres in diamond has recently been used for the in situ detection of pressure-induced phase transitions. However, owing to their four orientation axes and temperature-dependent zero-field splitting, interpreting these optically detected magnetic resonance spectra remains challenging. Here we study the optical and spin properties of implanted silicon vacancy defects in 4H-silicon carbide that exhibit single-axis and temperature-independent zero-field splitting. Using this technique, we observe the magnetic phase transition of Nd2Fe14B at about 7 GPa and map the critical temperature-pressure phase diagram of the superconductor YBa2Cu3O6.6. These results highlight the potential of silicon vacancy-based quantum sensors for in situ magnetic detection at high pressures.