高压下氢基高温超导体研究的新进展

赵文迪; 段德芳; 崔田

doi:10.11858/gywlxb.20210727

高压下氢基高温超导体研究的新进展

doi: 10.11858/gywlxb.20210727

赵文迪^1,,
段德芳^2,*, ,,
崔田^{1, 2,*, ,}

1.
宁波大学物理科学与技术学院，浙江宁波　315211
2.
吉林大学物理学院，吉林长春　130012

基金项目: 国家自然科学基金（51632002, 52072188, 11674122）；教育部长江学者和创新团队发展计划（IRT_15R23）

详细信息

作者简介:
赵文迪（1996－），男，硕士研究生，主要从事高压下氢基高温超导材料的结构与性质研究. E-mail：zwendi@yeah.net

通讯作者:
段德芳（1982－），女，博士，教授，主要从事高压下富氢超导材料的计算机模拟研究. E-mail：duandf@jlu.edu.cn

崔　田（1964－），男，博士，教授，主要从事高压下凝聚态物质结构与性质研究. E-mail：cuitian@nbu.edu.cn

中图分类号: O521.2
计量
- 文章访问数: 7872
- HTML全文浏览量: 2808
- PDF下载量: 217
出版历程
- 收稿日期: 2021-02-28
- 修回日期: 2021-03-14

New Developments of Hydrogen-Based High-Temperature Superconductors under High Pressure

ZHAO Wendi^1
,,
DUAN Defang^{2,*
, ,},
CUI Tian^{1, 2,*
, ,}

1.
School of Physical Science and Technology, Ningbo University, Ningbo 315211, Zhejiang, China
2.
College of Physics, Jilin University, Changchun 130012, Jilin, China

摘要

摘要: 富氢材料被认为是室温超导体的最佳候选体系，是物理学、材料科学等多学科的热点研究领域之一。理论和实验研究发现的新型共价氢化物H₃S和笼状氢化物LaH₁₀的超导转变温度（T_c）均超过 200 K，进一步推动了对富氢化合物超导电性的探索。最近，通过高压实验合成的碳质硫氢化物在288 K的室温下实现了零电阻，让人们看到了室温超导的曙光。本文结合课题组在此领域的主要成果，介绍了3类典型富氢化合物的结构及超导特性，包括近期首次在层状氢化物中发现的具有类五角石墨烯结构的富氢超导体HfH₁₀，其超导转变温度高达213～234 K。
- 高压 /
- 富氢材料 /
- 层状氢化物 /
- 超导电性
Abstract: Hydrogen-rich materials are considered to be the most potential candidates for room-temperature superconductors, yielding a research hotspot in physics, material science and so on. Remarkably, the new covalent hydride H₃S and clathrate like LaH₁₀, exhibit record high superconducting transition temperature (T_c) above 200 K both found theoretically and experimentally, which further promotes the study on the superconductivity of hydrogen-rich compounds. Very recently, the successful experimental discovery of high-temperature superconductivity at 288 K in a carbonaceous sulfur hydride system at high pressure shows the light for achieving room-temperature superconductors. In this paper, we introduce the structures and superconductivities of three typical hydrogen-rich compounds, including HfH₁₀, a "pentagraphenelike" superconductor exhibiting an extraordinarily high T_c of around 213–234 K at 250 GPa, which was recently discovered for the first time in layered structure hydrides.
- high pressure /
- hydrogen-rich material /
- layered hydrides /
- superconductivity

HTML全文

图 1 （a）200 GPa下Im${\overline{3}} $m-H₃S的晶体结构^[13]，（b）Im${\overline{3}} $m-H₃S (100) 晶面的二维电子局域函数^[13]

Figure 1. (a) Im${\overline{3}} $m-H₃S structure at 200 GPa^[13], (b) the calculated electron localization function of Im${\overline{3}} $m-H₃S for (100) plane^[13]

下载: 全尺寸图片幻灯片

图 2 （a）Fm${\overline{3}} $m-LaH₁₀结构中的H₃₂笼状结构^[17]，（b）P6₃/mmc-CeH₉结构中的H₂₉笼状结构^[44]，（c）各二元富氢化物中的最近邻氢原子距离与金属氢中最近邻氢原子距离的比较^[44]

Figure 2. (a) The H₃₂ cage in Fm${\overline{3}} $m-LaH₁₀^[17], (b) the H₂₉ cage in P6₃/mmc-CeH₉^[44], (c) the evolution of nearest-neighbor H-H distances in polyhydrides and atomic metallic H₂ as a function of pressure^[44]

下载: 全尺寸图片幻灯片

图 3 （a）P6₃/mmc-HfH₁₀的层状晶体结构^[33]，（b）P6₃/mmc-HfH₁₀的单层结构^[33]

Figure 3. (a) The crystal structure of layered P6₃/mmc in HfH₁₀^[33], (b) a layer of the P6₃/mmc-HfH₁₀ structure^[33]

下载: 全尺寸图片幻灯片

表 1 3类高T_c氢化物中氢的结构类型、金属的原子半径、电负性、价电子排布、晶体结构对称性以及对应压力点下超导电性的对比^[33]

Table 1. Comparison of structural types, atomic radius, electronegativity, electronic configuration, crystal structure symmetry and superconductivity of H in three types of high T_c hydrides^[33]

Hydrogenic motifs	Hydrides	Atomic radius/Å	Electronegativity	Electronic configuration	Space group	T_c/K
	H₃S	1.84	2.58	[Ne] 3s²3p⁴	Im${\overline{3}} $m	204^a (200 GPa)^[13], 203^b (155 GPa)^[28]
	H₃Se	1.98	2.55	[Ne] 3d¹⁰4s²4p⁴	Im${\overline{3}} $m	110^a (200 GPa)^[52]
	LaH₁₀	1.88	1.10	[Xe] 5d¹6s²	Fm${\overline{3}} $m	288^a (200 GPa)^[18], 250–260^b (170–200 GPa)^{[31, 30]}
	YH₁₀	1.81	1.22	[Kr] 4d¹5s²	Fm${\overline{3}} $m	303^a (400 GPa)^[18]
	ThH₁₀	1.80	1.30	[Rn] 6d²7s²	Fm${\overline{3}} $m	241^a (100 GPa)^[19], 161^b (174 GPa)^[32]
	HfH₁₀	1.56	1.30	[Xe] 4f¹⁴5d²6s²	P6₃/mmc	234^c (250 GPa)
	ZrH₁₀	1.60	1.33	[Kr] 4d²5s²	P6₃/mmc	220^c (250 GPa)
	ScH₁₀	1.61	1.36	[Ar] 3d¹4s²	P6₃/mmc	158^c (250 GPa)
	LuH₁₀	1.73	1.27	[Xe] 4f¹⁴5d¹6s²	P6₃/mmc	152^c (200 GPa)
Note : (1) The superscript “a” denotes the calculated T_c with fixed $\;\mu ^$ = 0.1 ($\;\mu ^$ is the coulomb parameter); (2) The superscript “b” denotes the experimental T_c in previous work; (3) The superscript “c” denotes the obtained T_c using G-K equation with $\;\mu ^*$ = 0.1.

下载: 导出CSV

参考文献(52)

[1]	BEDNORZ J G, MÜLLER K A. Possible high T_c superconductivity in the Ba-La-Cu-O system [J]. Zeitschrift für Physik B Condensed Matter, 1986, 64(2): 189–193. doi: 10.1007/BF01303701
[2]	GAO L, XUE Y Y, CHEN F, et al. Superconductivity up to 164 K in HgBa₂Ca_m-1Cu_mO_{2 m+2+ δ} (m = 1, 2, and 3) under quasihydrostatic pressures [J]. Physical Review B, 1994, 50(6): 4260–4263. doi: 10.1103/PhysRevB.50.4260
[3]	WU G, XIE Y L, CHEN H, et al. Superconductivity at 56 K in samarium-doped SrFeAsF [J]. Journal of Physics: Condensed Matter, 2009, 21(14): 142203. doi: 10.1088/0953-8984/21/14/142203
[4]	WIGNER E, HUNTINGTON H B. On the possibility of a metallic modification of hydrogen [J]. Journal of Chemical Physics, 1935, 3(12): 764–770. doi: 10.1063/1.1749590
[5]	BARDEEN J, COOPER L N, SCHRIEFFER J R. Theory of superconductivity [J]. Physical Review, 1957, 108(5): 1175–1204. doi: 10.1103/PhysRev.108.1175
[6]	DALLADAY-SIMPSON P, HOWIE R T, GREGORYANZ E. Evidence for a new phase of dense hydrogen above 325 gigapascals [J]. Nature, 2016, 529(7584): 63–67. doi: 10.1038/nature16164
[7]	LOUBEYRE P, OCCELLI F, DUMAS P. Synchrotron infrared spectroscopic evidence of the probable transition to metal hydrogen [J]. Nature, 2020, 577(7792): 631–635. doi: 10.1038/s41586-019-1927-3
[8]	ASHCROFT N W. Hydrogen dominant metallic alloys: high temperature superconductors? [J]. Physical Review Letters, 2004, 92(18): 187002. doi: 10.1103/PhysRevLett.92.187002
[9]	DUAN D F, LIU Y X, MA Y B, et al. Structure and superconductivity of hydrides at high pressures [J]. National Science Review, 2017, 4(1): 121–135. doi: 10.1093/nsr/nww029
[10]	DUAN D F, YU H Y, XIE H, et al. Ab initio approach and its impact on superconductivity [J]. Journal of Superconductivity and Novel Magnetism, 2019, 32(1): 53–60. doi: 10.1007/s10948-018-4900-8
[11]	EREMETS M I, TROJAN I A, MEDVEDEV S A, et al. Superconductivity in hydrogen dominant materials: silane [J]. Science, 2008, 319(5869): 1506–1509. doi: 10.1126/science.1153282
[12]	GONCHARENKO I, EREMETS M I, HANFLAND M, et al. Pressure-induced hydrogen-dominant metallic state in aluminum hydride [J]. Physical Review Letters, 2008, 100(4): 045504. doi: 10.1103/PhysRevLett.100.045504
[13]	DUAN D F, LIU Y X, TIAN F B, et al. Pressure-induced metallization of dense (H₂S)₂H₂ with high-T_c superconductivity [J]. Scientific Reports, 2014, 4: 6968. doi: 10.1038/srep06968
[14]	DUAN D F, HUANG X L, TIAN F B, et al. Pressure-induced decomposition of solid hydrogen sulfide [J]. Physical Review B, 2015, 91(18): 180502. doi: 10.1103/PhysRevB.91.180502
[15]	WANG H, TSE J S, TANAKA K, et al. Superconductive sodalite-like clathrate calcium hydride at high pressures [J]. Proceedings of the National Academy of Sciences of the United States of America, 2012, 109(17): 6463–6466. doi: 10.1073/pnas.1118168109
[16]	LI Y W, HAO J, LIU H Y, et al. Pressure-stabilized superconductive yttrium hydrides [J]. Scientific Reports, 2015, 5: 9948. doi: 10.1038/srep09948
[17]	LIU H Y, NAUMOV I I, HOFFMANN R, et al. Potential high-T_c superconducting lanthanum and yttrium hydrides at high pressure [J]. Proceedings of the National Academy of Sciences of the United States of America, 2017, 114(27): 6990–6995. doi: 10.1073/pnas.1704505114
[18]	PENG F, SUN Y, PICKARD C J, et al. Hydrogen clathrate structures in rare earth hydrides at high pressures: possible route to room-temperature superconductivity [J]. Physical Review Letters, 2017, 119(10): 107001. doi: 10.1103/PhysRevLett.119.107001
[19]	KVASHNIN A G, SEMENOK D V, KRUGLOV I A, et al. High-temperature superconductivity in a Th-H system under pressure conditions [J]. ACS Applied Materials & Interfaces, 2018, 10(50): 43809–43816. doi: 10.1021/acsami.8b17100
[20]	JIN X L, MENG X, HE Z, et al. Superconducting high-pressure phases of disilane [J]. Proceedings of the National Academy of Sciences of the United States of America, 2010, 107(22): 9969–9973. doi: 10.1073/pnas.1005242107
[21]	TROYAN I, GAVRILIUK A, RÜFFER R, et al. Observation of superconductivity in hydrogen sulfide from nuclear resonant scattering [J]. Science, 2016, 351(6279): 1303–1306. doi: 10.1126/science.aac8176
[22]	DUAN D F, TIAN F B, LIU Y X, et al. Enhancement of T_c in the atomic phase of iodine-doped hydrogen at high pressures [J]. Physical Chemistry Chemical Physics, 2015, 17(48): 32335–32340. doi: 10.1039/C5CP05218A
[23]	DUAN D F, HUANG X L, TIAN F B, et al. Predicted formation of H $$ in solid halogen polyhydrides at high pressures [J]. The Journal of Physical Chemistry A, 2015, 119(45): 11059–11065. doi: 10.1021/acs.jpca.5b08183
[24]	SHAO Z J, HUANG Y P, DUAN D F, et al. Stable structures and superconductivity of an At-H system at high pressure [J]. Physical Chemistry Chemical Physics, 2018, 20(38): 24783–24789. doi: 10.1039/C8CP04317E
[25]	WANG L Y, DUAN D F, YU H Y, et al. High-pressure formation of cobalt polyhydrides: a first-principle study [J]. Inorganic Chemistry, 2018, 57(1): 181–186. doi: 10.1021/acs.inorgchem.7b02371
[26]	SHAO Z J, DUAN D F, MA Y B, et al. Ternary superconducting cophosphorus hydrides stabilized via lithium [J]. NPG Computational Materials, 2019, 5(1): 104. doi: 10.1038/s41524-019-0244-6
[27]	SONG H, DUAN D F, CUI T, et al. High-T_c state of lanthanum hydrides [J]. Physical Review B, 2020, 102(1): 014510. doi: 10.1103/PhysRevB.102.014510
[28]	DROZDOV A P, EREMETS M I, TROYAN I A, et al. Conventional superconductivity at 203 kelvin at high pressures in the sulfur hydride system [J]. Nature, 2015, 525(7567): 73–76. doi: 10.1038/nature14964
[29]	EINAGA M, SAKATA M, ISHIKAWA T, et al. Crystal structure of the superconducting phase of sulfur hydride [J]. Nature Physics, 2016, 12(9): 835–838. doi: 10.1038/nphys3760
[30]	SOMAYAZULU M, AHART M, MISHRA A K, et al. Evidence for superconductivity above 260 K in lanthanum superhydride at megabar pressures [J]. Physical Review Letters, 2019, 122(2): 027001. doi: 10.1103/PhysRevLett.122.027001
[31]	DROZDOV A P, KONG P P, MINKOV V S, et al. Superconductivity at 250 K in lanthanum hydride under high pressures [J]. Nature, 2019, 569(7757): 528–531. doi: 10.1038/s41586-019-1201-8
[32]	SEMENOK D V, KVASHNIN A G, IVANOVA A G, et al. Superconductivity at 161 K in thorium hydride ThH₁₀: synthesis and properties [J]. Materials Today, 2020, 33: 36–44. doi: 10.1016/j.mattod.2019.10.005
[33]	XIE H, YAO Y S, FENG X L, et al. Hydrogen pentagraphenelike structure stabilized by hafnium: a high-temperature conventional superconductor [J]. Physical Review Letters, 2020, 125(21): 217001. doi: 10.1103/PhysRevLett.125.217001
[34]	STROBEL T A, GANESH P, SOMAYAZULU M, et al. Novel cooperative interactions and structural ordering in H₂S-H₂ [J]. Physical Review Letters, 2011, 107(25): 255503. doi: 10.1103/PhysRevLett.107.255503
[35]	HUANG X L, WANG X, DUAN D F, et al. High-temperature superconductivity in sulfur hydride evidenced by alternating-current magnetic susceptibility [J]. National Science Review, 2019, 6(4): 713–718. doi: 10.1093/nsr/nwz061
[36]	ALEXANDER F, GONCHAROV S S, LOBANOV V B, et al. Stable high-pressure phases in the H-S system determined by chemically reacting hydrogen and sulfur [J]. Physical Review B, 2017, 95(14): 140101. doi: 10.1103/PhysRevB.95.140101
[37]	PAPACONSTANTOPOULOS D A, KLEIN B M, MEHL M J, et al. Cubic H₃S around 200 GPa: an atomic hydrogen superconductor stabilized by sulfur [J]. Physical Review B, 2015, 91(18): 184511. doi: 10.1103/PhysRevB.91.184511
[38]	QUAN Y D, PICKETT W E. Van hove singularities and spectral smearing in high-temperature superconducting H₃S [J]. Physical Review B, 2016, 93(10): 104526. doi: 10.1103/PhysRevB.93.104526
[39]	HEIL C, BOERI L. Influence of bonding on superconductivity in high-pressure hydrides [J]. Physical Review B, 2015, 92(6): 060508. doi: 10.1103/PhysRevB.92.060508
[40]	GE Y F, ZHANG F, YAO Y G. First-principles demonstration of superconductivity at 280 K in hydrogen sulfide with low phosphorus substitution [J]. Physical Review B, 2016, 93(22): 224513. doi: 10.1103/PhysRevB.93.224513
[41]	SNIDER E, DASENBROCK-GAMMON N, MCBRIDE R, et al. Room-temperature superconductivity in a carbonaceous sulfur hydride [J]. Nature, 2020, 586(7829): 373–377. doi: 10.1038/s41586-020-2801-z
[42]	SUN Y, TIAN Y F, JIANG B W, et al. Computational discovery of a dynamically stable cubic SH₃-like high-temperature superconductor at 100 GPa via CH₄ intercalation [J]. Physical Review B, 2020, 101: 174102. doi: 10.1103/PhysRevB.101.174102
[43]	CUI W W, BI T G, SHI J M, et al. Route to high-T_c superconductivity via CH₄-intercalated H₃S hydride perovskites [J]. Physical Review B, 2020, 101(13): 134504. doi: 10.1103/PhysRevB.101.134504
[44]	LI X, HUANG X L, DUAN D F, et al. Polyhydride CeH₉ with an atomic-like hydrogen clathrate structure [J]. Nature Communications, 2019, 10(1): 3461. doi: 10.1038/s41467-019-11330-6
[45]	ZHOU D, SEMENOK D V, DUAN D F, et al. Superconducting praseodymium superhydrides [J]. Science Advances, 2020, 6(9): eaax6849. doi: 10.1126/sciadv.aax6849
[46]	ZHOU D, SEMENOK D V, XIE H, et al. High-pressure synthesis of magnetic neodymium polyhydrides [J]. Journal of the American Chemical Society, 2020, 142(6): 2803–2811. doi: 10.1021/jacs.9b10439
[47]	SHAO Z J, DUAN D, MA Y, et al. Unique phase diagram and superconductivity of calcium hydrides at high pressures [J]. Inorganic Chemistry, 2019, 58(4): 2558–2564. doi: 10.1021/acs.inorgchem.8b03165
[48]	WU G, HUANG X L, XIE H, et al. Unexpected calcium polyhydride CaH₄: a possible route to dissociation of hydrogen molecules [J]. The Journal of Chemical Physics, 2019, 150(4): 044507. doi: 10.1063/1.5053650
[49]	PÉPIN C M, GENESTE G, DEWAELE A, et al. Synthesis of FeH₅: a layered structure with atomic hydrogen slabs [J]. Science, 2017, 357(6349): 382–385. doi: 10.1126/science.aan0961
[50]	ZHONG X, WANG H, ZHANG J R, et al. Tellurium hydrides at high pressures: high-temperature superconductors [J]. Physical Review Letters, 2016, 116(5): 057002. doi: 10.1103/PhysRevLett.116.057002
[51]	ZHOU D W, JIN X L, MENG X, et al. Ab initio study revealing a layered structure in hydrogen-rich KH₆ under high pressure [J]. Physical Review B, 2012, 86(1): 014118. doi: 10.1103/PhysRevB.86.014118
[52]	ZHANG S, WANG Y, ZHANG J, et al. Phase diagram and high-temperature superconductivity of compressed selenium hydrides [J]. Scientific Reports, 2015, 5(3): 1–6.