Pressure-induced Superconductivity Research Articles

Two pressure-induced molecular superconductors with different types of crystal and electronic structures derived from an unsymmetrical tetrachalcogenafulvalene

Abstract We newly synthesized an organic donor molecule ETTM-STF (ethylenedithio(trimethylene)diselenadithiafulvalene), a molecular hybrid of HMTTF (hexamethylenetetrathiafulvalene) and BETS (bis(ethylenedithio)tetraselenafulvalene). Electrochemical oxidation of ETTM-STF provided two cation radical salts, (ETTM-STF)2Au(CN)2 and (ETTM-STF)2BF4. Crystal structure of the Au(CN)2 salt is characterized by a monolayer structure based on dimerized donor molecules. On the other hand, the BF4 salt shows a bilayer structure that is composed of two crystallographically independent conducting layers with different types of electronic structures. At ambient pressure, the Au(CN)2 salt is a Mott insulator and the BF4 salt undergoes a metal–nonmetal transition where the two types of conducting layers exhibit different behavior. Application of pressure suppressed the nonconducting behavior and induced a superconducting state in the Au(CN)2 salt (Tc = 3.4 K at 9.5 kbar) and in the BF4 salt (Tc = 6.8 K at 8 kbar).

Pressure-induced structural transition and superconductivity in hard compound IrB4

The recent discovery of MoB2 with a superconducting transition temperature (Tc) of up to 32 K at 100 GPa provides new insights into the metallization and subsequently high-Tc superconductivity of diborides, highlighting the potential of transition metals in these compounds. We herein re-evaluated the structure, mechanical, and superconducting properties of IrB4 under pressure up to 300 GPa using first-principles. Our calculations reveal that a new P21/c phase exhibiting a hardness of 15.75 GPa surpasses the stability of the C2/m structure identified through the particle swarm optimization at ambient pressure. Upon compressing, the P21/c phase transforms into an MgB2-type structure with a space group of P63/mmc at 62.5 GPa and then into the orthorhombic Cmca phase above 109 GPa. Unlike semiconductor behavior of the atmospheric pressure phase, the two high-pressure structures are metallic and superconducting, with Tc values of 29.90 for P63/mmc at 62.5 GPa and 13.45 K for Cmca at 125 GPa. Analysis of the electronic structure and electron–phonon coupling (EPC) reveals that the high Tc, similar to MgB2-type MoB2, stems from the Van Hove Singularities (VHS) near the Fermi level donated by transition metal Ir. The effect further enhances the EPC based on the boron contribution. More interestingly, pressure has little impacts on the position of the VHS. These findings provide a new platform for designing advanced high-Tc superconductors.

First-principles study on pressure-induced superconductivity and structural design on transition metal diborides.

Recent experiments on α-MoB2 with MgB2-type structure achieved superconductivity at ∼32K under 90GPa, the highest among transition-metal diborides, rekindling interest in their superconducting properties. Our study systematically investigates the band structures of AlB2-type transition metal diborides. We found that the superior superconductivity of MoB2, WB2, and TcB2 correlates with their von Hove singularities near the Fermi level (EF), potentially linked to electron-phonon coupling. These three diborides exhibit similar critical temperature (Tc) trends under pressure: rising initially, peaking around 60GPa, and then declining. While unstable at ambient pressure, their thermodynamic and dynamical stability limits vary significantly, possibly explaining experimental discrepancies. To stabilize MoB2 at ambient pressure, we designed MoXB4 compounds (X = other transition metals) by substituting every other Mo layer in MoB2 with an X layer. This modification aims to stabilize the structure and enhance superconductivity by reducing d-electron concentration at EF. This principle extends to other potential superconducting diborides, such as WB2 and TcB2. Using Nb as an example, we found that Nb atoms in AlB2-type MoNbB4 may exhibit random occupancy, potentially explaining disparities between theoretical predictions and experimental results. Our study offers valuable insights into superconductivity in transition metal diborides, paving the way for future research and applications.

Accelerating the calculation of electron-phonon coupling strength with machine learning.

The calculation of electron-phonon couplings (EPCs) is essential for understanding various fundamental physical properties, including electrical transport, optical and superconducting behaviors in materials. However, obtaining EPCs through fully first-principles methods is notably challenging, particularly for large systems or when employing advanced functionals. Here we introduce a machine learning framework to accelerate EPC calculations by utilizing atomic orbital-based Hamiltonian matrices and gradients predicted by an equivariant graph neural network. We demonstrate that our method not only yields EPC values in close agreement with first-principles results but also enhances calculation efficiency by several orders of magnitude. Application to GaAs using the Heyd-Scuseria-Ernzerhof functional reveals the necessity of advanced functionals for accurate carrier mobility predictions, while for the large Kagome crystal CsV3Sb5, our framework reproduces the experimentally observed double domes in pressure-induced superconducting phase diagrams. This machine learning framework offers a powerful and efficient tool for the investigation of diverse EPC-related phenomena in complex materials.

Pressure-induced superconductivity domes described with a theoretical equation based on the free volume concept

A generic conductivity equation developed in our previous work is borrowed to explore how superconductivity transition temperature changes with external high pressure. The volume-pressure relationship revealed in the literature is utilized to estimate the pressure-dependent free volume based on our free volume equation. Pressure-induced single and double superconductivity domes are predicted with the obtained equation. It is also used to fit experimental data available in the literature. A good agreement with experimental observations is obtained. Our equation can fit nonlinear and polynomial relationships as well. The findings provide a theoretical foundation for pressure-induced phenomena among many superconductors.

Structural phase transition and potential superconductivity initiated by pressure-driven in 1T–CrSe2

The exploration of the superconducting properties of antiferromagnetic parent compounds containing transition metals under pressure provides a unique idea for finding and designing superconducting materials with better performance. In this paper, the close relationship between the possible superconductivity and structure phase transition of the typical van der Waals layered material 1 T–CrSe2 induced by pressure is studied by means of electrical transport and x-ray diffraction for the first time. We introduce the possibility of pressure-induced superconductivity at 20 GPa, with a critical T c of approximately at 4 K. The superconductivity persists up to the highest measured pressure of 70 GPa, with a maximum T c ∼ 5 K at 24 GPa. We observed a structure phase transition from P-3 m1 to C2/m space group in the range of 9.4–11.7 GPa. The results show that the structural phase transition leads to the metallization of 1 T–CrSe2 and the further pressure effect makes the superconductivity appear in the new structure. The material undergoes a transition from a two-dimensional layered structure to a three-dimensional structure under pressure. This is the first time that possible superconductivity has been observed in 1 T–CrSe2.

Pressure-Induced Exciton Formation and Superconductivity in Platinum-Based Mineral Sperrylite.

We report a comprehensive study of Sperrylite (PtAs2), the main platinum source in natural minerals, as a function of applied pressures up to 150 GPa. While no structural phase transition is detected from pressure-dependent X-ray measurements, the unit cell volume shrinks monotonically with pressure following the third-order Birch-Murnaghan equation of state. The mildly semiconducting behavior found in pure synthesized crystals at ambient pressures becomes more insulating upon increasing the applied pressure before metalizing at higher pressures, giving way to the appearance of an abrupt decrease in resistance near 3 K at pressures above 92 GPa consistent with the onset of a superconducing phase. The pressure evolution of the calculated electronic band structure reveals the same physical trend as our transport measurements, with a non-monotonic evolution explained by a hole band that is pushed below the Fermi energy and an electron band that approaches it as a function of pressure, both reaching a touching point suggestive of an excitonic state. A Lifshitz transition of the electronic structure and an increase in the density of states may naturally explain the onset of superconductivity in this material.

Pressure-Induced Alloying and Superconductivity in GeTe

Pressure-Induced Alloying and Superconductivity in GeTe

Crystallographic parameters and their systematics within the CeCuAl3-related family of intermetallics

Rare-earth RTX3 compounds (T stands for a transition d-metal and X is a p-metal) form a large family of intermetallics, revealing a variety of intriguing physical properties. Among them, CeTX3 compounds represent a particularly studied group, due to their frequently complex magnetic structures, Kondo physics, pressure-induced superconductivity, or recently highlighted quantum quasi-bound states. We report on the structural properties and their systematics within the CeCuAl3-related intermetallics crystallising in the tetragonal structure of the BaNiSn3-type. Our synchrotron X-ray diffraction data of 14 selected alloys allow us to follow the evolution of crystallographic parameters of the CeCuAl3-based substitution series. Substitutions of R, T and X elements are shown to have significant impact on the unit cell volume, virtual lattice expansion and free fraction coordinates of individual Wyckoff sites. Structural parameters are discussed within the framework of physical properties of investigated compounds.

Strain-mediated phase crossover in Ruddlesden–Popper nickelates

Recent progress on the signatures of pressure-induced high-temperature superconductivity in Ruddlesden–Popper (RP) nickelates (Lan+1NinO3n+1) has attracted growing interest in both theoretical calculations and experimental efforts. The fabrication of high-quality single-crystalline RP nickelate thin films is critical for possible reducing the superconducting transition pressure and advancing applications in microelectronics in the future. In this study, we report the observations of an active phase transition in RP nickelate films induced by misfit strain. We found that RP nickelate films favor the perovskite structure (n = ∞) under tensile strains, while compressive strains stabilize the La3Ni2O7 (n = 2) phase. The selection of distinct phases is governed by the strain dependent formation energy and electronic configuration. In compressively strained La3Ni2O7, we experimentally determined the eg splitting energy is ~0.2 eV and electrons prefer to occupy in-plane orbitals. First-principles calculations unveil a robust coupling between strain effects and the valence state of Ni ions in RP nickelates, suggesting a dual driving force for the inevitable phase co-existence transition in RP nickelates. Our work underscores the sensitivity of RP nickelate formation to epitaxial strain, presenting a significant challenge in fabricating pure-phase RP nickelate films. Therefore, special attention to stacking defects and grain boundaries between different RP phases is essential when discussing the pressure-induced superconductivity in RP nickelates.

Tuning the Flat Band in Bi2O2Se by Pressure to Induce Superconductivity.

The discovery of superconductivity in twisted bilayer graphene has reignited enthusiasm in the field of flat-band superconductivity. However, important challenges remain, such as constructing a flat-band structure and inducing a superconducting state in materials. Here, we successfully achieved superconductivity in Bi2O2Se by pressure-tuning the flat-band electronic structure. Experimental measurements combined with theoretical calculations reveal that the occurrence of pressure-induced superconductivity at 30 GPa is associated with a flat-band electronic structure near the Fermi level. Moreover, in Bi2O2Se, a van Hove singularity is observed at the Fermi level alongside pronounced Fermi surface nesting. These remarkable features play a crucial role in promoting strong electron-phonon interactions, thus potentially enhancing the superconducting properties of the material. These findings demonstrate that pressure offers a potential experimental strategy for precisely tuning the flat band and achieving superconductivity.

Pressure-induced superconductivity in SnSb2Te4

Owing to their unique compositional and structural characteristics, layered van der Waals solids in binary and ternary chalcogenide families provide a fertile testbed for exploring novel exotic structures and states, e.g., topological insulators and superconductors. Herein, a comprehensive study on the structural variations and correlated electrical transport behavior of SnSb2Te4, a ternary member, has been carried out considering elevated pressures. Under 45.6 GPa, three distinct structural phase transitions have been observed, with strong evidence from the variations of high-pressure X-ray diffraction patterns. The onsets of phase II (monoclinic, C2/m ) at 6.3 GPa, phase III (monoclinic, C2/c ) at 15.5 GPa, and phase IV (body-centered cubic with substitutional disorder, Im-3m ) at 17.2 GPa have been observed owing to the emergence of new diffractions. Based on electrical measurements at low temperature and high pressure conditions, two pressure-induced superconducting states have been distinguished in SnSb2Te4. The first state occurs in the range of 12.3-17.1 GPa. The positive pressure dependence on Tc indicates that the aforementioned state is related to the monoclinic C2/m phase. At > 17.1 GPa, the second superconducting state emerges, with the negative pressure dependence on Tc . It relates to the body-centered cubic solid solution phase, which is characteristic of a substitutional disordered crystal structure. The discovery that the pressure-induced superconductivity in SnSb2Te4 is affected by structural phase transitions under pressure may help understand the universal relationship between the ambient condition topological insulating state and derived superconductivity. Ab initio theoretical calculations reveal that an electronic topological transition takes place at approximately 2.0 GPa, which is featured by the obvious changes in the distribution of electronic density of states near the Fermi level.

Distinct superconducting states in the pressure-induced metallic structures of topological heterostructure BiTe

The (Bi2)m(Bi2Te3)n homologous series possess natural multilayer heterostructure with intriguing physical properties at ambient pressure. Herein, we report the pressure-dependent evolution of the structure and electrical transport of the dual topological insulator BiTe, a member of the (Bi2)m(Bi2Te3)n series. With applied pressure, BiTe exhibits several different crystal structures and distinct superconducting states, which is remarkably similar to other members of the (Bi2)m(Bi2Te3)n series. Our results provide a systematic phase diagram for the pressure-induced superconductivity in BiTe, contributing to the highly interesting physics in this (Bi2)m(Bi2Te3)n series.

Pressure-induced superconductivity and robust Tc against external pressure in (Ge,Sn,Pb)Te

The robustness of superconducting transition temperature (Tc) against external pressure in medium entropy alloy (MEA) and high entropy alloy (HEA) -type compounds has attracted significant interest with regards to the realization of stable superconducting applications. In this study, we have synthesized Ge1/3Sn1/3Pb1/3Te belonging to MEA-type MTe, where the M site comprises only isovalent group-14 elements, to depict a critical factor for the robustness of Tc. High-pressure electrical transport measurements and structural analysis reveal that the high-pressure phase of CsCl-type cubic structure exhibits the robustness of Tc against external pressure. Molecular dynamics simulation and density functional theory calculation suggest that the glassy atomic vibration characteristic mainly contributes to the appearance of the robustness. This insight accelerates the further development of unique properties within HEA superconductors and their applications.

Pressure-induced Lifshitz transition in the type-II Weyl semimetal WP2

We report evidences of a pressure-induced Lifshitz transition in the type-II Weyl semimetal WP2 via resistance, synchrotron X-ray diffraction, and Raman scattering measurements with the aid of density functional theory calculations up to 50 GPa. The resistance at 2 K and 300 K and residual resistance ratio rise precipitously at ca. 20 GPa. The pristine orthorhombic structure is robust against pressures up to 50 GPa. There occurs a discontinuity in the unit cell volume, lattice parameter, lattice parameter ratio and axial compressibility at ～20 GPa. Two Raman-active modes soften abruptly accompanied with appearance of a new Raman-active mode at ～15 GPa. Density functional theory calculations identify drastic changes in the Fermi surface topology at～30 GPa. Our findings stimulate further pursuit of pressure-induced superconductivity via a Lifshitz transition in WP2.

Superconductivity of barium with highest transition temperatures in metallic materials at ambient pressure

Pressure-induced superconductivity often occurs following structural transition under hydrostatic pressure (PHP) but disappears after the pressure is released. In the alkali-earth metal barium, superconductivity appears after structural transformation from body-centered cubic structure to hexagonal-close-packed (hcp) structure at PHP = 5 GPa, and the superconducting transition temperature (Tc) reaches a maximum of 5 K at PHP = 18 GPa. Furthermore, by stabilizing the low-temperature phase at PHP ~ 30 GPa, Tc reached a higher level of 8 K. Herein, we demonstrate a significantly higher Tc superconductivity in Ba even at ambient pressure. This was made possible through severe plastic deformation of high-pressure torsion (HPT). In this HPT-processed Ba, we observed superconductivity at Tc = 3 K and Tc = 24 K in the quasi-stabilized hcp and orthorhombic structures, respectively. In particular, the latter Tc represents the highest value achieved at ambient pressure among single-element superconducting metals, including intermetallics. The phenomenon is attributed to a strained high-pressure phase, stabilized by residual strains generated from lattice defects such as dislocations and grain boundaries. Significantly, the observed Tc far exceeds predictions from DFT calculations under normal hydrostatic compressions. The study demonstrates the importance of utilizing high-pressure strained phases as quasi-stable superconducting states at ambient pressure.

Pressure-induced superconductivity in a novel germanium allotrope

High-pressure studies on elements play an essential role in superconductivity research, with implications for both fundamental science and applications. Here we report the experimental discovery of surprisingly low pressure driving a novel germanium allotrope into a superconducting state in comparison to that for α-Ge. Raman measurements revealed structural phase transitions and possible electronic topological transitions under pressure up to 58 GPa. Based on pressure-dependent resistivity measurements, superconductivity was induced above 2 GPa and the maximum Tc of 6.8 K was observed under 4.6 GPa. Interestingly, a superconductivity enhancement was discovered during decompression, indicating the possibility of maintaining pressure-induced superconductivity at ambient pressure with better superconducting performance. Density functional theory analysis further suggested that the electronic structure of Ge (oP32) is sensitive to its detailed geometry and revealed that disorder in the β-tin structure leads to a higher Tc in comparison to the perfect β-tin Ge.

Pressure-induced hydrogen-dominant high-temperature superconductors.

The century-old pursuit of room temperature superconductivity has finally been reached in highly compressed hydrogen-dominant compounds. Future efforts will be focused on understanding the high-pressure hydrogen physics and ambient-pressure applications.

Discovery of Unconventional Pressure-Induced Superconductivity in CrAs

Discovery of Unconventional Pressure-Induced Superconductivity in CrAs

Effects of pressure and doping on Ruddlesden-Popper phases Lan+1NinO3n+1

Recently, the discovery of superconductivity with a critical temperature Tc up to 80 K in Ruddlesden–Popper phases Lan+1NinO3n+1 (n = 2) under pressure has garnered considerable attention. Up to now, the superconductivity was only observed in La3Ni2O7 single crystal grown with the optical-image floating zone furnace under oxygen pressure. It remains to be understood the effect of chemical doping on superconducting La3Ni2O7 as well as other Ruddlesden–Popper phases. Here, we systematically investigate the effect of external pressure and chemical doping on polycrystalline Ruddlesden–Popper phases. Our results demonstrate that the application of pressure and doping effectively tunes the transport properties of Ruddlesden–Popper phases. We find pressure-induced superconductivity up to 86 K in La3Ni2O7 polycrystalline sample, while no signatures of superconductivity are observed in La2NiO4 and La4Ni3O10 polycrystalline samples under high pressure up to 50 GPa. Our study sheds light on the exploration of high-Tc superconductivity in nickelates.