arXiv subjects

Russell J. Hemley

Publications and source records attributed to Russell J. Hemley.

At least 37 records · Page 2Linked to original sources

arXiv2022

Structure and equation of state of $Bi_2Sr_2Ca_{n-1}Cu_nO_{2n+4+δ}$ from x-ray diffraction to megabar pressures

Pressure is a unique tuning parameter for probing the properties of materials and has been particularly useful for studies of electronic materials such as high-temperature cuprate superconductors. Here we report the effects of quasi-hydrostatic compression produced by a neon pressure-medium on the structures of bismuth-based high $\mathit{T_c}$ cuprate superconductors with the nominal composition $Bi_2Sr_2Ca_{n-1}Cu_nO_{2n+4+δ}$ (n=1,2,3) up to 155 GPa. The structures of all three compositions obtained by synchrotron X-ray diffraction can be described as pseudo-tetragonal over the entire pressure range studied. We show that previously reported pressure-induced distortions and structural changes arise from the large strains that can be induced in these layered materials by non-hydrostatic stresses. The pressure-volume equations of state (EOS) measured under these quasi-hydrostatic conditions cannot be fit to single phenomenological formulation over the pressure ranges studied, starting below 20 GPa. This intrinsic anomalous compression as well as the sensitivity of $Bi_2Sr_2Ca_{n-1}Cu_nO_{2n+4+δ}$ to deviatoric stresses provides explanations for the numerous inconsistencies in reported EOS parameters for these materials. We conclude that the anomalous compressional behavior of all three compositions is a manifestation of the changes in electronic properties that are also responsible for the remarkable non-monotonic dependence of $\mathit{T_c}$ with pressure, including the increase in $\mathit{T_c}$ at the highest pressures studied so far for each. Transport and spectroscopic measurements up to megabar pressures are needed to fully characterize and explore still higher possible critical temperatures in these materials.

cond-mat.supr-con↗

arXiv2022

Unified chemical theory of structure and bonding in elemental metals

Most elemental metals under ambient conditions adopt simple structures such as BCC, FCC and HCP in specific groupings across the Periodic Table, and on compression, many of these elements undergo transitions to surprisingly complex structures, including open and low-symmetry phases not expected from conventional free-electron based theories of metals. First-principles calculations have been able to reproduce many observed structures and transitions, but a unified, predictive theory of bonding that underlies this behavior is not yet in hand. We propose a remarkably simple theory based on large-scale high-throughput calculations of the elements over a broad range of thermodynamic conditions. The results broaden the conventional concept of metallic bonding with a new perspective that both explains the stability of different simple structures as well as lower symmetry phases arising from electron localization at interstitial sites in these structures. The success of this simple framework reveals the important role of chemical interactions in governing the structures and electronic properties of simple metals.

cond-mat.mtrl-sci↗

arXiv2021

A Little Bit of Carbon Can do a Lot for Superconductivity in H$_3$S

First-principles calculations were carried out to provide a chemical basis for proposed structures associated with the recently reported room-temperature superconductivity in a carbonaceous sulfur hydride material under pressure. Calculations were performed on supercells of H$_3$S doped with 1.85-25\% carbon, corresponding to SH$_3$~$\rightarrow$~CH$_3$ or SH$_3$~$\rightarrow$~CH$_4$ substitutions, primarily at pressures of 270 GPa where the maximum critical temperature, $T_c$, has been reported. In the first type of substitution, the carbon atoms can be six-fold coordinated, stabilizing a CH$_6$ configuration within the cubic H$_3$S framework structure that forms under pressure. In the second, the carbon can be four-fold coordinated as methane intercalated into the H-S lattice, with or without an additional hydrogen in the framework. The results indicate that unusual local bonding configurations with respect to carbon can be stabilized under pressure. The doping breaks degenerate bands, lowering the density of states at the Fermi level ($N_F$), and localizing electrons in C-H bonds. Low levels of CH$_4$ doping do not increase $N_F$ to values as high as those calculated for $Im\bar{3}m$ H$_3$S, but they do result in a larger logarithmic average phonon frequency, and an electron-phonon coupling parameter comparable to that of $R3m$ H$_3$S. The $T_c$s estimated for carbon doping levels ranging from 1.85-5.7\% are compatible with experimental measurements for the C-S-H superconductor.

cond-mat.supr-con↗

arXiv2021

Prediction of high-Tc superconductivity in ternary lanthanum borohydrides

The study of superconductivity in compressed hydrides is of great interest due to measurements of high critical temperatures (Tc) in the vicinity of room temperature, beginning with the observations of LaH10 at 170-190 GPa. However, the pressures required for synthesis of these high Tc superconducting hydrides currently remain extremely high. Here we show the investigation of crystal structures and superconductivity in the La-B-H system under pressure with particle-swarm intelligence structure searches methods in combination with first-principles calculations. Structures with six stoichiometries, LaBH, LaBH3, LaBH4, LaBH6, LaBH7 and LaBH8, were predicted to become stable under pressure. Remarkably, the hydrogen atoms in LaBH8 were found to bond with B atoms in a manner that is similar to that in H3S. Lattice dynamics calculations indicate that LaBH7 and LaBH8 become dynamically stable at pressures as low as 109.2 and 48.3 GPa, respectively. Moreover, the two phases were predicted to be superconducting with a critical temperature (Tc) of 93 K and 156 K at 110 GPa and 55 GPa, respectively. Our results provide guidance for future experiments targeting new hydride superconductors with both low synthesis pressures and high Tc.

cond-mat.mtrl-sci↗

arXiv2021

X-ray Diffraction and Equation of State of the C-S-H Room-Temperature Superconductor

X-ray diffraction indicates that the structure of the recently discovered room temperature carbonaceous sulfur hydride (C-S-H) superconductor is derived from previously established van der Waals compounds found in the H$_2$S-H$_2$ and CH$_4$-H$_2$ systems. Crystals of the superconducting phase were produced by a photochemical synthesis technique leading to the superconducting critical temperature $T_c$ of 288 K at 267 GPa. Single-crystal x-ray diffraction patterns measured from 124 to 178 GPa, within the pressure range of the superconducting phase, give an orthorhombic structure derived from the Al$_2$Cu-type determined for (H$_2$S)$_2$H$_2$ and (CH$_4$)$_2$H$_2$ that differs from those predicted and observed for the S-H system to these pressures. The formation and stability of the C-S-H compound can be understood in terms of the close similarity in effective volumes of the H$_2$S and CH$_4$ components over a broad range of pressures. The relative amounts of carbon and sulfur in the structure is not determined, and denser carbon-bearing S-H structures may form at higher pressures. The results are consistent with hole-doping enhancement of $T_c$ by carbon proposed for the room-temperature superconductivity in this system.

cond-mat.supr-con↗

arXiv2020

The Li-F-H Ternary System at High Pressures

Evolutionary crystal structure prediction searches have been employed to explore the ternary Li-F-H system at 300 GPa. Metastable phases were uncovered within the static lattice approximation, with LiF$_3$H$_2$, LiF$_2$H, Li$_3$F$_4$H, LiF$_4$H$_4$, Li$_2$F$_3$H and LiF$_3$H lying within 50 meV/atom of the 0 K convex hull. All of these phases contain H$_n$F$_{n+1}^-$ ($n$ = 1; 2) anions, and Li$^+$ cations. Other structural motifs such as LiF slabs, H$_3^+$ molecules, and F$^{δ-}$ ions are present in some of the low enthalpy Li-F-H structures. The bonding within the H$_n$F$_{n+1}^-$ molecules, which may be bent or linear, symmetric or asymmetric, is analyzed. The five phases closest to the hull are insulators, while LiF$_3$H is metallic and predicted to have a vanishingly small superconducting critical temperature. This study lays the foundation for future investigations of the role of temperature and anharmonicity on the stability and properties of compounds and alloys in the Li-F-H ternary system.

cond-mat.mtrl-sci↗

arXiv2020

Room-Temperature Superconductivity in Boron-Nitrogen Doped Lanthanum Superhydride

Recent theoretical and experimental studies of hydrogen-rich materials at megabar pressures (i.e., >100 GPa) have led to the discovery of very high-temperature superconductivity in these materials. Lanthanum superhydride LaH$_{10}$ has been of particular focus as the first material to exhibit a superconducting critical temperature (T$_c$) near room temperature. Experiments indicate that the use of ammonia borane as the hydrogen source can increase the conductivity onset temperatures of lanthanum superhydride to as high as 290 K. Here we examine the doping effects of B and N atoms on the superconductivity of LaH$_{10}$ in its fcc (Fm-3m) clathrate structure at megabar pressures. Doping at H atomic positions strengthens the H$_{32}$ cages of the structure to give higher phonon frequencies that enhance the Debye frequency and thus the calculated T$_c$. The predicted T$_c$ can reach 288 K in LaH$_{9.985}$N$_{0.015}$ within the average high-symmetry structure at 240 GPa.

cond-mat.supr-con↗

arXiv2020

Hole-Doped Room-Temperature Superconductivity in H$_{3}$S$_{1-x}$Z$_x$ (Z=C, Si)

We examine the effects of the low-level substitution of S atoms by C and Si atoms on the superconductivity of H$_3$S with the $Im\bar{3}m$ structure at megabar pressure. The hole doping can fine-tune the Fermi energy to reach the electronic density-of-states peak maximizing the electron-phonon coupling. This can boost the critical temperature from the original 203 K to 289 K and 283 K, respectively, for H$_3$S$_{0.962}$C$_{0.038}$ at 260 GPa and H$_3$S$_{0.960}$Si$_{0.040}$ at 230 GPa. The former may provide an explanation for the recent experimental observation of room-temperature superconductivity in a highly compressed C-S-H system [Nature 586, 373-377 (2020)]. Our work opens a new avenue for substantially raising the critical temperatures of hydrogen-rich materials.

cond-mat.supr-con↗

arXiv2020

$\mathcal{P}^2$: Combining pressure and electrochemistry to synthesize superhydrides

Recently, superhydrides have been computationally identified and subsequently synthesized with a variety of metals at very high pressures. In this work, we evaluate the possibility of synthesizing superhydrides by uniquely combining electrochemistry and applied pressure. We perform computational searches for palladium superhydrides using density functional theory and particle swarm optimization calculations over a broad range of pressures and electrode potentials. We incorporate exchange-correlation functional uncertainty using the Bayesian error estimation formalism to quantify the uncertainty associated with the identified stable phases. Based on a thermodynamic analysis, we construct pressure-potential phase diagrams and provide an alternate synthesis concept, $\mathcal{P}^2$ (pressure-potential), to accessing novel phases having high hydrogen content. Palladium-hydrogen is a widely-studied material system with the highest hydride phase being Pd$_3$H$_4$. Most strikingly for this system, at potentials above hydrogen evolution and $\sim$300 MPa pressure, we find the possibility to make palladium superhydrides (e.g., PdH$_{10}$). We demonstrate the generalizability of this approach for La-H, Y-H and Mg-H with 10-100 fold reduction in required pressure for stabilizing phases. In addition, the $\mathcal{P}^2$ strategy allows stabilizing new phases that cannot be done purely by either pressure or potential and is a general approach that is likely to work for synthesizing other superhydrides at modest pressures.

cond-mat.mtrl-sci↗

arXiv2019

Road to Room-Temperature Superconductivity: Tc above 260 K in Lanthanum Superhydride under Pressure

The use of high pressure to realize superconductivity in the vicinity of room temperature has a long history, much of it focused on achieving this in hydrogen rich materials. This paper provides a brief overview of the work presented at this May 2018 conference, together with background on motivation and techniques, the theoretical predictions of superconductivity in lanthanum hydride, and the subsequent experimental confirmation. Theoretical calculations using density functional based structure search methods combined with BCS type models predicted a new class of dense, hydrogen rich materials superhydrides with superconducting critical temperatures in the vicinity of room temperature at and above 200 GPa pressures. The existence of a series of these phases in the La H system was subsequently confirmed experimentally, and techniques were developed for their syntheses and characterization, including measurements of structural and transport properties, at megabar pressures. Four probe electrical transport measurements of a cubic phase identified as LaH10 display signatures of superconductivity at temperatures above 260 K near 200 GPa. The results are supported by pseudo four probe conductivity measurements, critical current determinations, low-temperature xray diffraction, and magnetic susceptibility measurements. The measured high Tc is in excellent agreement with the original calculations. The experiments also reveal additional superconducting phases with Tc between 150 K and above 260 K. This effort highlights the novel physics in hydrogen-rich materials at high densities, the success of materials by design in the discovery and creation of new materials, and the possibility of new classes of superconductors Tc at and above room temperature.

cond-mat.supr-con↗

arXiv2018

Evidence for superconductivity above 260 K in lanthanum superhydride at megabar pressures

Recent predictions and experimental observations of high Tc superconductivity in hydrogen-rich materials at very high pressures are driving the search for superconductivity in the vicinity of room temperature. We have developed a novel preparation technique that is optimally suited for megabar pressure syntheses of superhydrides using pulsed laser heating while maintaining the integrity of sample-probe contacts for electrical transport measurements to 200 GPa. We detail the synthesis and characterization, including four-probe electrical transport measurements, of lanthanum superhydride samples that display a significant drop in resistivity on cooling beginning around 260 K and pressures of 190 GPa. Additional measurements on two additional samples synthesized the same way show resistance drops beginning as high as 280 K at these pressures. The loss of resistance at these high temperatures is not observed in control experiments on pure La as well as in partially transformed samples at these pressures, and x-ray diffraction as a function of temperature on the superhydride reveal no structural changes on cooling. We infer that the resistance drop is a signature of the predicted room-temperature superconductivity in LaH10, in good agreement with density functional structure search and BCS theory calculations.

cond-mat.mtrl-sci↗

arXiv2017

Synthesis of Polar Ordered Oxynitride Perovskite

For decades, numerous attempts have been made to produce polar oxynitride perovskites, where some of the oxygen are replaced by nitrogen, but a polar ordered oxynitride has never been demonstrated. Caracas and Cohen studied possible ordered polar oxynitrides within density functional theory (DFT) and found a few candidates that were predicted to be insulating and at least metastable. YSiO2N stood out with huge predicted polarization and nonlinear optic coefficients. In this study, we demonstrate the synthesis of perovskite-structured YSiO2N by using a combination of a diamond anvil cell and in-situ laser heating technique. Subsequent in-situ X-ray diffraction, second harmonic generation, and Raman scattering measurements confirm that it is polar and a strong nonlinear optical material, with structure and properties similar to those predicted by DFT.

cond-mat.mtrl-sci↗

arXiv2016

Topological surface states in dense solid hydrogen

It has recently been established that two-dimensional massless graphene-like systems and three-dimensional line-node topological semimetals comprise a special class of centrosymmetric materials where edge/surface states of topological nature inevitably appear in some k-regions. We show that the phases of solid hydrogen produced at megabar pressures can be line-node topological semimetals. In such phases, the material exhibits topological surface states and therefore can be a poor bulk metal but good surface conductor. The results may help to explain discrepant high-pressure experimental data reported for dense hydrogen as well as provide predictions for future measurements, including possible surface superconductivity in hydrogen. Related topological behavior may be expected in high-pressure phases formed in other elements including simple metals.

cond-mat.mtrl-sci↗

arXiv2014

Crystal field and related phenomena in hexagonal close-packed H2 and D2 under pressure

The lattice distortion parameter (the deviation of the c/a ratio from the ideal value 1.633), orientational order parameter, and crystal-field parameter in hexagonal close-packed (hcp) lattice of p-H2, o-D2 and n-H2 are calculated using the semi-empirical lattice-dynamic approach. It is shown that the lattice distortion in the J-even species is two order of magnitude smaller compared with that found in n-H2, and n-D2. The difference is due to the splitting of the J-odd rotational levels in the J-even - J-odd mixtures.

cond-mat.mtrl-sci↗

arXiv2013

Electronic properties and metrology of the diamond NV- center under pressure

The negatively charged nitrogen-vacancy (NV-) center in diamond has realized new frontiers in quantum technology. Here, the center's optical and spin resonances are observed under hydrostatic pressures up to 60 GPa. Our observations motivate powerful new techniques to measure pressure and image high pressure magnetic and electric phenomena. Our observations further reveal a fundamental inadequacy of the current model of the center and provide new insight into its electronic structure.

cond-mat.mtrl-sci↗

arXiv2013

Graphene physics and insulator-metal transition in compressed hydrogen

Compressed hydrogen passes through a series of layered structures in which the layers can be viewed as distorted graphene sheets. The electronic structures of these layered structures can be understood by studying simple model systems- an ideal single hydrogen graphene sheet and three-dimensional model lattices consisting of such sheets. The energetically stable structures result from structural distortions of model graphene-based systems due to electronic instabilities towards Peierls or other distortions associated with the opening of a band gap. Two factors play crucial roles in the metallization of compressed hydrogen: (i) crossing of conduction and valence bands in hexagonal or graphene-like layers due to topology and (ii) formation of bonding states with $2p_z$ $π$ character.

cond-mat.mtrl-sci↗

arXiv2013

High-pressure effects on single crystals electron-doped r$_{2-x}$Ce$_{x}$CuO$_{4}$

We present high pressure diamond anvil cell synchrotron X-ray, resistivity, and ac-susceptibility measurements on electron-doped cuprate Pr$_{2-x}$Ce$_{x}$CuO$_{4}$ to much higher pressures than previously reported. At 2.72 GPa between 88 and 98$%$ of the superconducting T$^\prime$ phase \cite{Tprime} of the optimally doped Pr$_{1.85}$Ce$_{0.15}$CuO$_{4}$ transforms into the insulating phase T. The T$_{c}$ of the remaining 2-12$%$ T$^\prime$ phase is suppressed continuously from 22 K to 18.5 K at about 14 GPa. Remarkably, the T$_{c}$ of the over doped Pr$_{1.83}$Ce$_{0.17}$CuO$_{4}$ remains practically unchanged even at 32 GPa. This behavior of the electron-doped cuprate contrasts with that of the hole-doped cuprate for which T$_{c}$ is first substantially enhanced with applied pressure.

cond-mat.supr-con↗

arXiv2012

Pressure dependence of the monoclinic phase in (1-x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 solid solutions

We combine high-pressure x-ray diffraction, high-pressure Raman scattering, and optical microscope to investigate a series of PMN-xPT solid solutions (x=0.2, 0.3, 0.33, 0.35, 0.37, 0.4) in diamond anvil cells up to 20 GPa at 300 K. The Raman spectra show a peak centered at 380 cm-1 above 6 GPa for all samples, in agreement with previous observations. X-ray diffraction measurements are consistent with this spectral change indicating structural phase transition; we find that the triplet at the pseudo cubic (220) Bragg peak merges into a doublet above 6 GPa. Our results indicate that the morphotropic phase boundary region (x=0.33 to 0.37) with the presence of monoclinic symmetry persists up to 7 GPa. The pressure dependence of ferroelectric domains in PMN-0.32PT single crystals was observed using a polarizing optical microscope. The domain wall density decreases with pressure and domains disappear at a modest pressure of 3 GPa. We propose a pressure-composition phase diagram for PMN-xPT solid solutions.

cond-mat.mtrl-sci↗