A superconductor is a material that can conduct electricity without resistance below a superconducting transition temperature, Tc. The highest Tc that has been achieved to date is in the copper oxide system: 133 kelvin at ambient pressure and 164 kelvin at high pressures. As the nature of superconductivity in these materials is still not fully understood (they are not conventional superconductors), the prospects for achieving still higher transition temperatures by this route are not clear. In contrast, the Bardeen-Cooper-Schrieffer theory of conventional superconductivity gives a guide for achieving high Tc with no theoretical upper bound--all that is needed is a favourable combination of high-frequency phonons, strong electron-phonon coupling, and a high density of states. These conditions can in principle be fulfilled for metallic hydrogen and covalent compounds dominated by hydrogen, as hydrogen atoms provide the necessary high-frequency phonon modes as well as the strong electron-phonon coupling. Numerous calculations support this idea and have predicted transition temperatures in the range 50-235 kelvin for many hydrides, but only a moderate Tc of 17 kelvin has been observed experimentally. Here we investigate sulfur hydride, where a Tc of 80 kelvin has been predicted. We find that this system transforms to a metal at a pressure of approximately 90 gigapascals. On cooling, we see signatures of superconductivity: a sharp drop of the resistivity to zero and a decrease of the transition temperature with magnetic field, with magnetic susceptibility measurements confirming a Tc of 203 kelvin. Moreover, a pronounced isotope shift of Tc in sulfur deuteride is suggestive of an electron-phonon mechanism of superconductivity that is consistent with the Bardeen-Cooper-Schrieffer scenario. We argue that the phase responsible for high-Tc superconductivity in this system is likely to be H3S, formed from H2S by decomposition under pressure. These findings raise hope for the prospects for achieving room-temperature superconductivity in other hydrogen-based materials.

Conventional superconductivity at 203 kelvin at high pressures in the sulfur hydride system

Hydrogen-rich superhydrides are believed to be very promising high-Tc superconductors. Recent experiments discovered superhydrides at very high pressures, e.g. FeH5 at 130 GPa and LaH10 at 170 GPa. With the motivation of discovering new hydrogen-rich high-Tc superconductors at lowest possible pressure, here we report the prediction and experimental synthesis of cerium superhydride CeH9 at 80–100 GPa in the laser-heated diamond anvil cell coupled with synchrotron X-ray diffraction. Ab initio calculations were carried out to evaluate the detailed chemistry of the Ce-H system and to understand the structure, stability and superconductivity of CeH9. CeH9 crystallizes in a P63/mmc clathrate structure with a very dense 3-dimensional atomic hydrogen sublattice at 100 GPa. These findings shed a significant light on the search for superhydrides in close similarity with atomic hydrogen within a feasible pressure range. Discovery of superhydride CeH9 provides a practical platform to further investigate and understand conventional superconductivity in hydrogen rich superhydrides. Hydrogen-rich superhydrides are promising high-temperature superconductors which have been observed only at pressures above 170 GPa. Here the authors show that CeH9 can be synthesized at 80-100 GPa with laser heating, and is characterized by a clathrate structure with a dense 3-dimensional atomic hydrogen sublattice.

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Synthesis of clathrate cerium superhydride CeH9 at 80-100 GPa with atomic hydrogen sublattice.

Recent predictions and experimental observations of high T_{c} 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 modulated laser heating while maintaining the integrity of sample-probe contacts for electrical transport measurements to 200 GPa. We detail the synthesis and characterization of lanthanum superhydride samples, including four-probe electrical transport measurements that display significant drops in resistivity on cooling up to 260 K and 180-200 GPa, and resistivity transitions at both lower and higher temperatures in other experiments. Additional current-voltage measurements, critical current estimates, and low-temperature x-ray diffraction are also obtained. We suggest that the transitions represent signatures of superconductivity to near room temperature in phases of lanthanum superhydride, in good agreement with density functional structure search and BCS theory calculations.

https://link.aps.org/accepted/10.1103/PhysRevLett.122.027001

Evidence for Superconductivity above 260 K in Lanthanum Superhydride at Megabar Pressures

A systematic structure search in the La–H and Y–H systems under pressure reveals some hydrogen-rich structures with intriguing electronic properties. For example, LaH10 is found to adopt a sodalite-like face-centered cubic (fcc) structure, stable above 200 GPa, and LaH8 a C2/m space group structure. Phonon calculations indicate both are dynamically stable; electron phonon calculations coupled to Bardeen–Cooper–Schrieffer (BCS) arguments indicate they might be high-Tc superconductors. In particular, the superconducting transition temperature Tc calculated for LaH10 is 274–286 K at 210 GPa. Similar calculations for the Y–H system predict stability of the sodalite-like fcc YH10 and a Tc above room temperature, reaching 305–326 K at 250 GPa. The study suggests that dense hydrides consisting of these and related hydrogen polyhedral networks may represent new classes of potential very high-temperature superconductors.

Potential high-Tc superconducting lanthanum and yttrium hydrides at high pressure.

The highest critical temperature of superconductivity Tc has been achieved in cuprates: 133 K at ambient pressure and 164 K at high pressures. As the nature of superconductivity in these materials is still not disclosed, the prospects for a higher Tc are not clear. In contrast the Bardeen-Cooper-Schrieffer (BCS) theory gives a clear guide for achieving high Tc: it should be a favorable combination of high frequency phonons, strong coupling between electrons and phonons, and high density of states. These conditions can be fulfilled for metallic hydrogen and covalent hydrogen dominant compounds. Numerous followed calculations supported this idea and predicted Tc=100-235 K for many hydrides but only moderate Tc~17 K has been observed experimentally. Here we found that sulfur hydride transforms at P~90 GPa to metal and superconductor with Tc increasing with pressure to 150 K at ~200 GPa. This is in general agreement with recent calculations of Tc~80 K for H2S. Moreover we found superconductivity with Tc~190 K in a H2S sample pressurized to P>150 GPa at T>220 K. This superconductivity likely associates with the dissociation of H2S, and formation of SHn (n>2) hydrides. We proved occurrence of superconductivity by the drop of the resistivity at least 50 times lower than the copper resistivity, the decrease of Tc with magnetic field, and the strong isotope shift of Tc in D2S which evidences a major role of phonons in the superconductivity. H2S is a substance with a moderate content of hydrogen therefore high Tc can be expected in a wide range of hydrogen-contain materials. Hydrogen atoms seem to be essential to provide the high frequency modes in the phonon spectrum and the strong electron-phonon coupling.

Conventional superconductivity at 190 K at high pressures

The high pressure structures, metallization and superconductivity of recently synthesized H2-containing compounds (H2S)2H2 are elucidated by ab initio calculations. The ordered crystal structure with P1 symmetry is determined, supported by the good agreement between theoretical and experimental X-ray diffraction data, equation of states and Raman spectra. The Cccm structure is favorable with partial hydrogen bond symmetrization above 37 GPa. Upon further compression, H2 molecules disappear and two intriguing metallic structures with R3m and Im-3m symmetries are reconstructive above 111 and 180 GPa, respectively. The predicted metallization pressure is 111 GPa, which is approximately one-third of the currently suggested metallization pressure of bulk molecular hydrogen. Application of the Allen-Dynes-modified McMillan equation for the Im-3m structure yields high Tc values of 191 K to 204 K at 200 GPa, which is among the highest values reported for H2-rich van der Waals compounds and MH3 type hydride thus far.

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Pressure-induced metallization of dense (H2S)2H2 with high-Tc superconductivity

Solid hydrogen sulfide is a typical molecular crystal, but its stability under pressure remains controversial. In particular, the recent experimental discovery of high-pressure superconductivity at 190 K in an ${\mathrm{H}}_{2}\mathrm{S}$ sample (arXiv:1412.0460) inspired efforts to revalidate this controversial issue, the pressure at which ${\mathrm{H}}_{2}\mathrm{S}$ decomposes and the resultant decomposition products urgent need to be evaluated. In this paper we performed an extensive structural study on different stoichiometries of HnS with $ng1$ under high pressure using ab initio calculations. Our results show that ${\mathrm{H}}_{2}\mathrm{S}$ is stable below 43 GPa and at elevated pressure it decomposes into ${\mathrm{H}}_{3}\mathrm{S}$ and sulfur. ${\mathrm{H}}_{3}\mathrm{S}$ is stable at least up to 300 GPa, while other H-rich compounds, including ${\mathrm{H}}_{4}\mathrm{S}, {\mathrm{H}}_{5}\mathrm{S}$, and ${\mathrm{H}}_{6}\mathrm{S}$, are unstable in the pressure range of this study.

Pressure-induced decomposition of solid hydrogen sulfide

Hydrogen atoms can provide high phonon frequencies and strong electron-phonon coupling in hydrogen-rich materials, which are believed to be potential high-temperature superconductors at lower pressure than metallic hydrogen. Especially, recently both of theoretical and experimental reports on sulfur hydrides under pressure exhibiting superconductivity at temperatures as high as 200 K have further stimulated an intense search for room-temperature superconductors in hydrides. This review focuses on crystal structures, stabilities, pressure-induced transformations, metallization, and superconductivity of hydrogen-rich materials at high pressures.

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Structure and superconductivity of hydrides at high pressures

A preliminary investigation has been carried to evaluate the influence of Al content on the microstructures and mechanical properties of Mg–Al alloys in as-cast condition. Three types of Mg–Al alloys were studied and characterized by Mg–10Al–Zn, Mg–20Al–Zn and Mg–44Al, respectively. The results indicate that the microstructures of all three alloys mainly consist of α-Mg solid solution, β-Mg 17 Al 12 and the eutectic mixture (α-Mg + β-Mg 17 Al 12 ). Increasing the Al content leads to the microstructures changes and increase the micro-hardness of the Mg–Al alloys. When the Al content increases to 44 wt%, the main phase of the alloy is β-Mg 17 Al 12 and the micro-hardness reaches to about 280 (HV). The reasons for these changes were also discussed in this paper.

Yunxian Liu

Papers

Pressure-induced metallization of dense (H2S)2H2 with high-Tc superconductivity

Pressure-induced decomposition of solid hydrogen sulfide

Structure and superconductivity of hydrides at high pressures

Effect of Al content on the microstructures and mechanical properties of Mg–Al alloys

The microstructure and mechanical properties of Mg-3Al-3RE alloys