High T_c superconductivity in layered hydrides XH₁₅ (X = Ca, Sr, Y, La) under high pressures

Abstract

The theoretical predictions and experimental synthesis of H₃S and LaH₁₀ superconductors with record high superconducting transition temperatures (T_c) have promoted the hydrogen-based superconducors to be a research hotspot in the field of solid-state physics. Here, we predict an unprecedented layered structure CaH₁₅, with high T_c of 189 K at 200 GPa using ab initio calculations. As concerns the novel structure, one layer is made of a hydrogen nonagon, the other layer consists of a Ca atom and six H₂ molecular units surrounding the Ca atom. This layered structure was also found in SrH₁₅, YH₁₅, and LaH₁₅ at high pressures, each materials exhibit high T_c especially YH₁₅ can reach above 200 K at 220 GPa. It represents the second class of layered superhydrides with high value of T_c after pentagraphene like HfH₁₀.

Graphical abstract

Keywords

high pressure / hydrides / superconductivity / ab initio calculation

References

[1] J. M. McMahon , D. M. Ceperley . Ground-state structures of atomic metallic hydrogen. Phys. Rev. Lett., 2011, 106( 16): 165302

[2] J. Sun , M. Martinez-Canales , D. D. Klug , C. J. Pickard , R. J. Needs . Stable all-nitrogen metallic salt at terapascal pressures. Phys. Rev. Lett., 2013, 111( 17): 175502

[3] J. Sun , M. Martinez-Canales , D. D. Klug , C. J. Pickard , R. J. Needs . Persistence and eventual demise of oxygen molecules at terapascal pressures. Phys. Rev. Lett., 2012, 108( 4): 045503

[4] L. Zhu , Z. Wang , Y. Wang , G. Zou , H. K. Mao , Y. Ma . Spiral chain O₄ form of dense oxygen. Proc. Natl. Acad. Sci. USA, 2012, 109( 3): 751

[5] D. Duan , Z. Liu , Z. Lin , H. Song , H. Xie , T. Cui , C. J. Pickard , M. Miao . Multistep dissociation of fluorine molecules under extreme compression. Phys. Rev. Lett., 2021, 126( 22): 225704

[6] E. Wigner , H. B. Huntington . On the possibility of a metallic modification of hydrogen. J. Chem. Phys., 1935, 3( 12): 764

[7] N. W. Ashcroft . Metallic hydrogen: A high-temperature superconductor. Phys. Rev. Lett., 1968, 21( 26): 1748

[8] J. M. McMahon , D. M. Ceperley . High-temperature superconductivity in atomic metallic hydrogen. Phys. Rev. B, 2011, 84( 14): 144515

[9] R. P. Dias , I. F. Silvera . Observation of the Wigner−Huntington transition to metallic hydrogen. Science, 2017, 355( 6326): 715

[10] J. M. McMahon , D. M. Ceperley . Ground-state structures of atomic metallic hydrogen. Phys. Rev. Lett., 2011, 106( 16): 165302

[11] N. W. Ashcroft . Hydrogen dominant metallic alloys: High temperature superconductors. Phys. Rev. Lett., 2004, 92( 18): 187002

[12] L. Zhang , Y. Wang , J. Lv , Y. Ma . Materials discovery at high pressures. Nat. Rev. Mater., 2017, 2( 4): 17005

[13] M. Du , W. Zhao , T. Cui , D. Duan . Compressed superhydrides: The road to room temperature superconductivity. J. Phys.: Condens. Matter, 2022, 34( 17): 173001

[14] D. Duan , Y. Liu , Y. Ma , Z. Shao , B. Liu , T. Cui . Structure and superconductivity of hydrides at high pressures. Natl. Sci. Rev., 2017, 4( 1): 121

[15] X. H. Xiao , D. F. Duan , Y. B. Ma , H. Xie , H. Song , D. Li , F. B. Tian , B. B. Liu , H. Y. Yu , T. Cui . Ab initio studies of copper hydrides under high pressure. Front. Phys., 2019, 14( 4): 1

[16] L. P. Gor’kov , V. Z. Kresin . Colloquium: High pressure and road to room temperature superconductivity. Rev. Mod. Phys., 2018, 90( 1): 011001

[17] E. Zurek . Hydrides of the alkali metals and alkaline earth metals under pressure. Comments Inorg. Chem., 2017, 37( 2): 78

[18] Z. Zhang , T. Cui , M. J. Hutcheon , A. M. Shipley , H. Song , M. Du , V. Z. Kresin , D. Duan , C. J. Pickard , Y. Yao . Design principles for high-temperature superconductors with a hydrogen-based alloy backbone at moderate pressure. Phys. Rev. Lett., 2022, 128( 4): 047001

[19] D. Duan , Y. Liu , F. Tian , D. Li , X. Huang , Z. Zhao , H. Yu , B. Liu , W. Tian , T. Cui . Pressure-induced metallization of dense (H₂S)₂H₂ with high-T_c superconductivity. Sci. Rep., 2015, 4( 1): 6968

[20] D. Duan , X. Huang , F. Tian , D. Li , H. Yu , Y. Liu , Y. Ma , B. Liu , T. Cui . Pressure-induced decomposition of solid hydrogen sulfide. Phys. Rev. B, 2015, 91( 18): 180502

[21] H. Liu , I. I. Naumov , R. Hoffmann , N. W. Ashcroft , R. J. Hemley . Potential high-T_c superconducting lanthanum and yttrium hydrides at high pressure. Proc. Natl. Acad. Sci. USA, 2017, 114( 27): 6990

[22] F. Peng , Y. Sun , C. J. Pickard , R. J. Needs , Q. Wu , Y. Ma . Hydrogen clathrate structures in rare earth hydrides at high pressures: Possible route to room-temperature superconductivity. Phys. Rev. Lett., 2017, 119( 10): 107001

[23] A. P. Drozdov , M. I. Eremets , I. A. Troyan , V. Ksenofontov , S. I. Shylin . Conventional superconductivity at 203 kelvin at high pressures in the sulfur hydride system. Nature, 2015, 525( 7567): 73

[24] M. Einaga , M. Sakata , T. Ishikawa , K. Shimizu , M. I. Eremets , A. P. Drozdov , I. A. Troyan , N. Hirao , Y. Ohishi . Crystal structure of the superconducting phase of sulfur hydride. Nat. Phys., 2016, 12( 9): 835

[25] A. P. Drozdov , P. P. Kong , V. S. Minkov , S. P. Besedin , M. A. Kuzovnikov , S. Mozaffari , L. Balicas , F. F. Balakirev , D. E. Graf , V. B. Prakapenka , E. Greenberg , D. A. Knyazev , M. Tkacz , M. I. Eremets . Superconductivity at 250 K in lanthanum hydride under high pressures. Nature, 2019, 569( 7757): 528

[26] M. Somayazulu , M. Ahart , A. K. Mishra , Z. M. Geballe , M. Baldini , Y. Meng , V. V. Struzhkin , R. J. Hemley . Evidence for superconductivity above 260 K in lanthanum superhydride at megabar pressures. Phys. Rev. Lett., 2019, 122( 2): 027001

[27] Y. Li , J. Hao , H. Liu , J. Tse , Y. Wang , Y. Ma . Pressure-stabilized superconductive yttrium hydrides. Sci. Rep., 2015, 5( 1): 9948

[28] H. Song , Z. Zhang , T. Cui , C. J. Pickard , V. Z. Kresin , D. Duan . High T_c superconductivity in heavy rare earth hydrides. Chin. Phys. Lett., 2021, 38( 10): 107401

[29] X. Zhong Y. Sun T. Iitaka M. Xu H. Liu C. Chen Y. Ma, Potential room temperature superconductivity in clathrate lanthanide/actinides octadechydrides at extreme pressures, doi: 10.21203/rs.3.rs-1148583/v1 ( 2021)

[30] H. Xie , Y. Yao , X. Feng , D. Duan , H. Song , Z. Zhang , S. Jiang , S. A. T. Redfern , V. Z. Kresin , C. J. Pickard , T. Cui . Hydrogen pentagraphenelike structure stabilized by hafnium: A high-temperature conventional superconductor. Phys. Rev. Lett., 2020, 125( 21): 217001

[31] A. K. Mishra , T. Muramatsu , H. Liu , Z. M. Geballe , M. Somayazulu , M. Ahart , M. Baldini , Y. Meng , E. Zurek , R. J. Hemley . New calcium hydrides with mixed atomic and molecular hydrogen. J. Phys. Chem. C, 2018, 122( 34): 19370

[32] G. Wu , X. Huang , H. Xie , X. Li , M. Liu , Y. Liang , Y. Huang , D. Duan , F. Li , B. Liu , T. Cui . Unexpected calcium polyhydride CaH₄: A possible route to dissociation of hydrogen molecules. J. Chem. Phys., 2019, 150( 4): 044507

[33] H. Wang , J. S. Tse , K. Tanaka , T. Iitaka , Y. Ma . Superconductive sodalite-like clathrate calcium hydride at high pressures. Proc. Natl. Acad. Sci. USA, 2012, 109( 17): 6463

[34] L. Ma K. Wang Y. Xie X. Yang Y. Wang M. Zhou H. Liu G. Liu H. Wang Y. Ma, High- T_c superconductivity in clathrate calcium hydride CaH₆, arXiv: 2103.16282 (2021)

[35] Z. Shao , D. Duan , Y. Ma , H. Yu , H. Song , H. Xie , D. Li , F. Tian , B. Liu , T. Cui . Unique phase diagram and superconductivity of calcium hydrides at high pressures. Inorg. Chem., 2019, 58( 4): 2558

[36] D. V. Semenok , D. Zhou , A. G. Kvashnin , X. Huang , M. Galasso , I. A. Kruglov , A. G. Ivanova , A. G. Gavriliuk , W. Chen , N. V. Tkachenko , A. I. Boldyrev , I. Troyan , A. R. Oganov , T. Cui . Novel strongly correlated europium superhydrides. J. Phys. Chem. Lett., 2021, 12( 1): 32

[37] Y. Wang , H. Wang , J. S. Tse , T. Iitaka , Y. Ma . Structural morphologies of high-pressure polymorphs of strontium hydrides. Phys. Chem. Chem. Phys., 2015, 17( 29): 19379

[38] W. Chen , D. V. Semenok , A. G. Kvashnin , X. Huang , I. A. Kruglov , M. Galasso , H. Song , D. Duan , A. F. Goncharov , V. B. Prakapenka , A. R. Oganov , T. Cui . Synthesis of molecular metallic barium superhydride: Pseudocubic BaH₁₂. Nat. Commun., 2021, 12( 1): 273

[39] C. J. Pickard R. J. Needs, Ab initio random structure searching , J. Phys.: Condens. Matter 23(5), 053201 ( 2011)

[40] S. J. Clark , M. D. Segall , C. J. Pickard , P. J. Hasnip , M. J. Probert , K. Refson , M. C. Payne . First principles methods using CASTEP. Z. Kristallogr. Cryst. Mater., 2005, 220( 5−6): 567

[41] G. Kresse , J. Furthmuller . Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B, 1996, 54( 16): 11169

[42] P. Giannozzi S. Baroni N. Bonini M. Calandra R. Car C. Cavazzoni D. Ceresoli G. L. Chiarotti M. Cococcioni I. Dabo A. Dal Corso S. de Gironcoli S. Fabris G. Fratesi R. Gebauer U. Gerstmann C. Gougoussis A. Kokalj M. Lazzeri L. Martin-Samos N. Marzari F. Mauri R. Mazzarello S. Paolini A. Pasquarello L. Paulatto C. Sbraccia S. Scandolo G. Sclauzero A. P. Seitsonen A. Smogunov P. Umari R. M. Wentzcovitch, QUANTUM ESPRESSO: A modular and open-source software project for quantum simulations of materials, J. Phys.: Condens. Matter 21(39), 395502 ( 2009)

[43] W. L. McMillan . Transition temperature of strong-coupled superconductors. Phys. Rev., 1968, 167( 2): 331

[44] G. M. Eliashberg . Interactions between electrons and lattice vibrations in a superconductor. Sov. Phys. JETP, 1960, 11( 3): 696

[45] C. J. Pickard , R. J. Needs . Structure of phase III of solid hydrogen. Nat. Phys., 2007, 3( 7): 473

Note:

This paper is dedicated to the 70th anniversary of the physics of Jilin University.

Electronic supplementary materials

are available in the online version of this article at https://doi.org/10.1007/s11467-022-1182-1 and https://journal.hep.com.cn/fop/EN/10.1007/s11467-022-1182-1 and are accessible for authorized users. See Supplemental Material for the structural information, Bader charge analysis and band structures of CaH₁₅, enthalpy difference curves of CaH₁₂, structural information and crystal structure of CaH₁₄, as well as convex hull diagram of Sr–H, Y–H and La–H system under high pressures.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant Nos. 12122405, 52072188, and 51632002), the National Key R&D Program of China (Grant No. 2018YFA0305900), and the Jilin Provincial Science and Technology Development Project (20210509038RQ). Parts of the calculations were performed in the High Performance Computing Center (HPCC) of Jilin University and TianHe-1(A) at the National Supercomputer Center in Tianjin.

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