芳香超导体: 电-声耦合与电子关联

钟国华; 林海青

doi:10.7498/aps.72.20231751

摘要

芳香超导体是近年来发现的一类新型高温超导体, 超导转变温度随芳香分子尺寸的增大而升高, 这引起了的实验和理论研究的广泛关注. 关于其超导特性的驱动机制是电-声耦合还是电子关联效应等相关问题吸引了国内外研究组的极大兴趣. 本文简述了芳香超导体的研究进展, 介绍了金属掺杂芳香化合物后展现出的丰富超导现象, 从电-声耦合和电子关联角度, 讨论了国内外研究组对芳香化合物超导性的理解, 及其对探索具有更高转变温度的芳香高温超导体的意义, 最后介绍了目前领域内面临的挑战.

关键词:

Abstract

Aromatic superconductors are a new type of high-temperature superconductor discovered in recent years. The superconducting transition temperature (T_c) increases with the size of aromatic molecule increasing, which has attracted widespread attention of experimental and theoretical researchers. The driving mechanism for such a superconductivity, whether it is dominated by electron-phonon coupling or electronic correlation effects, has aroused great interest of many research groups. This paper briefly introduces the rich superconducting phenomena of metal doped aromatic compounds. From the perspectives of electron-phonon coupling or electronic correlations, the superconductivity of aromatic compounds is discussed, which is helpful in exploring aromatic superconductors with higher T_c. The challenges currently faced in the field are also introduced.The rest of this paper is organized as follows. We first introduce the existence of abundant superconducting phases in the experiment of metal doped aromatic compounds. Different doping concentrations of metal cause superconducting phases with different T_c values, especially the highest T_c value of the superconducting phase increases with the size of aromatic molecule increasing. Theoretical prediction shows that all aromatic hydrocarbon superconductors have a low-T_c superconducting phase in a range of 5–7 K, which is a common feature. For systems with few benzene rings (such as benzene, naphthalene, and phenanthrene crystals), only low-T_c phase of 5–7 K exists, while in systems with multiple benzene rings (such as picene, dibenzopentacene, and others with the number of benzene rings more than 5), there are multiple superconducting phases; the highest T_c in long-benzene-ring system depends not only on the number of benzene rings, but also on the chain size of organic molecule. Further research indicates that low-T_c phase is induced by doping about 2 electrons and has good stability, while high-T_c phase results from doping 3 electrons and has slightly poorer stability.Then, the electron-phonon coupling characteristics and electron-electron exchange correlation effects in aromatic compound superconductors are discussed. For low-T_c phases, the values of electronic density of states at the Fermi level are comparable to each other and relatively low, resulting in weak electron-phonon interactions. However, the T_c value predicted by this electron-phonon coupling mechanism is in good agreement with experimental value, indicating that the electron-phonon coupling is sufficient to describe the superconductivity of low-T_c phases. For high-T_c phases, the big values of electron density of states at the Fermi level imply strong electron-phonon interactions, and this electron-phonon coupling increases with the size of organic molecule increasing. However, the T_c value predicted only by the electron-phonon mechanism is lower than the experimental value. The study of electron-electron exchange correlation effect of aromatic compounds shows that the electronic correlation effect increases with the size of aromatic molecule increasing, which is consistent with the increase of T_c maximum value with the size of aromatic molecule increasing in a long-benzene-ring system. This indicates that the superconductivity of high-T_c phase is driven by both the electron-phonon mechanism and the electronic correlation effect. This understanding of superconductivity is significant for exploring and discovering aromatic superconductors with higher transition temperatures.Finally, comprehensive physical models and methods are required in this paper in order to gain a thorough understanding of the superconductivity of aromatic compound.

Keywords:

作者及机构信息

钟国华¹,
林海青²

1.
中国科学院深圳先进技术研究院, 深圳　518055

2.
浙江大学物理学院, 杭州　310058

通信作者: 林海青, hqlin@zju.edu.cn

基金项目: 国家自然科学基金(批准号: 12088101, 12074401)资助的课题.

Authors and contacts

Zhong Guo-Hua¹,
Lin Hai-Qing²

1.
Shenzhen Institute of Advanced Technology, Chinese Academy of Sciences, Shenzhen 518055, China

2.
School of Physics, Zhejiang University, Hangzhou 310058, China

Corresponding author: Lin Hai-Qing, hqlin@zju.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 12088101, 12074401).

文章全文 : translate this paragraph

参考文献

[1]	Schilling A, Cantoni M, Guo J D, Ott H R 1993 Nature 363 56 Google Scholar
[2]	Drozdov A P, Kong P P, Minkov V S, Besedin S P, Kuzovnikov M A, Mozaffari S, Balicas L, Balakirev F F, Graf D E, Prakapenka V B, Greenberg E, Knyazev D A, Tkacz M, Eremets M I 2019 Nature 569 528 Google Scholar
[3]	Somayazulu M, Ahart M, Mishra A K, Geballe Z M, Baldini M, Meng Y, Struzhkin V V, Hemley R J 2019 Phys. Rev. Lett. 122 027001 Google Scholar
[4]	Little W A 1964 Phys. Rev. 134 A1416 Google Scholar
[5]	Ginzburg V L 1964 Phys. Lett. 13 101 Google Scholar
[6]	Taniguchi H, Miyashita M, Uchiyama K, Satoh K, Mori N, Okamoto H, Miyagawa K, Kanoda K, Hedo M, Uwatoko Y 2003 J. Phys. Soc. Jpn. 72 468 Google Scholar
[7]	Mitsuhashi R, Suzuki Y, Yamanari Y, Mitamura H, Kambe T, Ikeda N, Okamoto H, Fujiwara A, Yamaji M, Kawasaki N, Maniwa Y, Kubozono Y 2010 Nature 464 76 Google Scholar
[8]	Wang X F, Liu R H, Gui Z, Xie Y L, Yan Y J, Ying J J, Luo X G, Chen X H 2011 Nat. Commun. 2 507 Google Scholar
[9]	Xue M Q, Cao T B, Wang D M, Wu Y, Yang H X, Dong X L, He J B, Li F W, Chen G F 2012 Sci. Rep. 2 389 Google Scholar
[10]	Kubozono Y, Mitamura M, Lee X, He X, Yamanari Y, Takahashi Y, Suzuki Y, Kaji Y, Eguchi R, Akaike K, Kambe T, Okamoto H, Fujiwara A, Kato T, Kosugi T, Aoki H 2011 Phys. Chem. Chem. Phys. 13 16476 Google Scholar
[11]	Zhong G H, Chen X J, Lin H Q 2019 Front. Phys. 7 52 Google Scholar
[12]	Kato T, Yoshizawa K, Hirao K 2002 J. Chem. Phys. 116 3420 Google Scholar
[13]	Kato T, Kambe T, Kubozono Y 2011 Phys. Rev. Lett. 107 077001 Google Scholar
[14]	Casula M, Calandra M, Profeta G, Mauri F 2011 Phys. Rev. Lett. 107 137006 Google Scholar
[15]	Giovannetti G, Capone M 2011 Phys. Rev. B 83 134508 Google Scholar
[16]	Kim M, Min B I 2011 Phys. Rev. B 83 214510 Google Scholar
[17]	Durand P, Darling G R, Dubitsky Y, Zaopo A, Rosseinsky M J 2003 Nature Mater. 2 605 Google Scholar
[18]	Wang X H, Zhong G H, Yan X W, Chen X J, Lin H Q 2017 J. Phys. Chem. Solids 104 56 Google Scholar
[19]	Zhong G H, Yang D Y, Zhang K, Wang R S, Zhang C, Lin H Q, Chen X J 2018 Phys. Chem. Chem. Phys. 20 25217 Google Scholar
[20]	Wang R S, Gao Y, Huang Z B, Chen X J 2017 Superconductivity in P-Terphenyl arXiv: 1703.05803
[21]	Yan J F, Zhong G H, Wang R S, Zhang K, Lin H Q, Chen X J 2019 J. Phys. Chem. Lett. 10 40 Google Scholar
[22]	Huang G, Zhong G H, Wang R S, Han J X, Lin H Q, Chen X J 2019 Carbon 143 837 Google Scholar
[23]	Wang R S, Cheng J, Wu X L, Yang H, Chen X J, Gao Y, Huang Z B 2018 J. Chem. Phys. 149 144502 Google Scholar
[24]	Peng D, Wang R S, Chen X J 2020 J. Phys. Chem. C 124 906 Google Scholar
[25]	Wang R S, Zhang K, Zhong G H, Chen X J 2023 Mater. Sci. Eng. B 288 116155 Google Scholar
[26]	Wang R S, Gao Y, Huang Z B, Chen X J 2017 Superconductivity at 43 K in a single C-C bond linked terphenyl arXiv: 1703.05804
[27]	Wang R S, Gao Y, Huang Z B, Chen X J 2017 Superconductivity above 120 Kelvin in a Chain Link Molecule arXiv: 1703.06641
[28]	Zhong G H, Wang X H, Wang R S, Han J X, Zhang C, Chen X J, Lin H Q 2018 J. Phys. Chem. C 122 3801 Google Scholar
[29]	Li H, Zhou X, Parham S, Nummy T, Griffith J, Gordon K N, Chronister E L, Dessau D S 2019 Phys. Rev. B 100 064511 Google Scholar
[30]	Neha P, Bhardwaj A, Sahu V, Patnaik S 2018 Physica C 554 1 Google Scholar
[31]	Liu W H, Lin H, Kang R Z, Zhu X Y, Zhang Y, Zheng S X, Wen H H 2017 Phys. Rev. B 96 224501 Google Scholar
[32]	Pinto N, Di Nicola C, Trapananti A, Minicucci M, Di Cicco A, Marcelli A, Bianconi A, Marchetti F, Pettinari C, Perali A 2020 Condens. Matter 5 78 Google Scholar

施引文献

图 1 (a) 超导转变温度T_c与芳香分子晶体中有机分子所含苯环数的关系^[9]; (b) 电-声耦合常数随有机分子中碳原子数的变化^[12]; (c) 电-声相互作用随有机分子中碳原子数的变化, 插图表示电-声相互作用与碳原子倒数呈线性关系^[13]

Fig. 1. (a) The relationship between the superconducting transition temperature T_c and the number of benzene rings in organic molecules in aromatic molecular crystals^[9]; (b) the variation of the electron-phonon coupling constant with the number of carbon atoms in organic molecules^[12]; (c) the electron-phonon interaction varies with the number of carbon atoms in organic molecules, and the inset shows a linear relationship between the electron-phonon interaction and the reciprocal of carbon atoms^[13].

下载: 全尺寸图片幻灯片

图 2 各种芳香分子晶体在金属掺杂后的超导转变温度T_c随苯环数n的变化^[11], 灰色区域暗示了5—7 K的超导转变温度区间, 实心红色方块表示林海青等^[11]的预测结果, 而空心红色方块表示Casula等^[14]的预测结果, 其他数据来自实验

Fig. 2. The superconducting transition temperature T_c of aromatic molecular crystals doped by metal varies with the number of benzene rings n ^[11]. The gray area indicates a superconducting transition temperature region of 5—7 K. The solid red squares represent the prediction results of Lin et al.^[11], while the hollow red squares represent the prediction results of Casula et al.^[14]. Other data come from experiments.

下载: 全尺寸图片幻灯片

图 3 在芳香分子晶体中, 有效在位库仑能与带宽的比值(U_eff/W)随介电常数的变化. 有机分子的右上标I指分子中苯环呈zigzag排列, II指有机分子构型类似于1, 2:8, 9-二苯并五苯^[11]

Fig. 3. In aromatic molecular crystals, the ratio of effective on-site Coulombic energy to bandwidth (U_eff/W) varies with the dielectric constant. The superscript I of organic molecules refers to the zigzag arrangement of the benzene rings in the molecule, while II refers to the configuration of organic molecules similar to 1, 2:8, 9-dibenzopentacene ^[11].

下载: 全尺寸图片幻灯片

表 1 采用标准的密度泛函(DFT)方法预测芳香有机分子晶体的带隙(E_g)小于实验值. 采用杂化密度泛函(HSE)方法预测获得与实验一致的带隙, 所需的精确交换作用参数υ. 有机分子的右上标I指分子中苯环呈zigzag排列, II指有机分子构型类似于1, 2:8, 9-二苯并五苯^[11]

Table 1. The band gap (E_g) of aromatic organic molecular crystals predicted by standard density functional theory (DFT) method is smaller than the experimental values. υ is the adopted precise exchange interaction parameters when obtaining the E_g which is consistent with experimental values. The superscript I of organic molecules refers to the zigzag arrangement of the benzene rings in the molecule, while II refers to the configuration of organic molecules similar to 1, 2:8, 9-dibenzopentacene ^[11].

C₁₄H₁₀^I C₁₈H₁₂^I(II) C₂₂H₁₄^I C₂₂H₁₄^II C₂₆H₁₆^I C₂₆H₁₆^II C₃₀H₁₈^I C₃₀H₁₈^II

E_g (expt.)/eV 3.16 3.3 3.3 3.3 3.15 3.2 3.2 3.2
E_g (DFT)/eV 2.80 2.40 2.31 2.20 2.07 1.82 2.04 1.03
υ 0.10 0.26 0.30 0.40 0.36 0.55 0.37 0.91

下载: 导出CSV

map

[1]	Schilling A, Cantoni M, Guo J D, Ott H R 1993 Nature 363 56 Google Scholar
[2]	Drozdov A P, Kong P P, Minkov V S, Besedin S P, Kuzovnikov M A, Mozaffari S, Balicas L, Balakirev F F, Graf D E, Prakapenka V B, Greenberg E, Knyazev D A, Tkacz M, Eremets M I 2019 Nature 569 528 Google Scholar
[3]	Somayazulu M, Ahart M, Mishra A K, Geballe Z M, Baldini M, Meng Y, Struzhkin V V, Hemley R J 2019 Phys. Rev. Lett. 122 027001 Google Scholar
[4]	Little W A 1964 Phys. Rev. 134 A1416 Google Scholar
[5]	Ginzburg V L 1964 Phys. Lett. 13 101 Google Scholar
[6]	Taniguchi H, Miyashita M, Uchiyama K, Satoh K, Mori N, Okamoto H, Miyagawa K, Kanoda K, Hedo M, Uwatoko Y 2003 J. Phys. Soc. Jpn. 72 468 Google Scholar
[7]	Mitsuhashi R, Suzuki Y, Yamanari Y, Mitamura H, Kambe T, Ikeda N, Okamoto H, Fujiwara A, Yamaji M, Kawasaki N, Maniwa Y, Kubozono Y 2010 Nature 464 76 Google Scholar
[8]	Wang X F, Liu R H, Gui Z, Xie Y L, Yan Y J, Ying J J, Luo X G, Chen X H 2011 Nat. Commun. 2 507 Google Scholar
[9]	Xue M Q, Cao T B, Wang D M, Wu Y, Yang H X, Dong X L, He J B, Li F W, Chen G F 2012 Sci. Rep. 2 389 Google Scholar
[10]	Kubozono Y, Mitamura M, Lee X, He X, Yamanari Y, Takahashi Y, Suzuki Y, Kaji Y, Eguchi R, Akaike K, Kambe T, Okamoto H, Fujiwara A, Kato T, Kosugi T, Aoki H 2011 Phys. Chem. Chem. Phys. 13 16476 Google Scholar
[11]	Zhong G H, Chen X J, Lin H Q 2019 Front. Phys. 7 52 Google Scholar
[12]	Kato T, Yoshizawa K, Hirao K 2002 J. Chem. Phys. 116 3420 Google Scholar
[13]	Kato T, Kambe T, Kubozono Y 2011 Phys. Rev. Lett. 107 077001 Google Scholar
[14]	Casula M, Calandra M, Profeta G, Mauri F 2011 Phys. Rev. Lett. 107 137006 Google Scholar
[15]	Giovannetti G, Capone M 2011 Phys. Rev. B 83 134508 Google Scholar
[16]	Kim M, Min B I 2011 Phys. Rev. B 83 214510 Google Scholar
[17]	Durand P, Darling G R, Dubitsky Y, Zaopo A, Rosseinsky M J 2003 Nature Mater. 2 605 Google Scholar
[18]	Wang X H, Zhong G H, Yan X W, Chen X J, Lin H Q 2017 J. Phys. Chem. Solids 104 56 Google Scholar
[19]	Zhong G H, Yang D Y, Zhang K, Wang R S, Zhang C, Lin H Q, Chen X J 2018 Phys. Chem. Chem. Phys. 20 25217 Google Scholar
[20]	Wang R S, Gao Y, Huang Z B, Chen X J 2017 Superconductivity in P-Terphenyl arXiv: 1703.05803
[21]	Yan J F, Zhong G H, Wang R S, Zhang K, Lin H Q, Chen X J 2019 J. Phys. Chem. Lett. 10 40 Google Scholar
[22]	Huang G, Zhong G H, Wang R S, Han J X, Lin H Q, Chen X J 2019 Carbon 143 837 Google Scholar
[23]	Wang R S, Cheng J, Wu X L, Yang H, Chen X J, Gao Y, Huang Z B 2018 J. Chem. Phys. 149 144502 Google Scholar
[24]	Peng D, Wang R S, Chen X J 2020 J. Phys. Chem. C 124 906 Google Scholar
[25]	Wang R S, Zhang K, Zhong G H, Chen X J 2023 Mater. Sci. Eng. B 288 116155 Google Scholar
[26]	Wang R S, Gao Y, Huang Z B, Chen X J 2017 Superconductivity at 43 K in a single C-C bond linked terphenyl arXiv: 1703.05804
[27]	Wang R S, Gao Y, Huang Z B, Chen X J 2017 Superconductivity above 120 Kelvin in a Chain Link Molecule arXiv: 1703.06641
[28]	Zhong G H, Wang X H, Wang R S, Han J X, Zhang C, Chen X J, Lin H Q 2018 J. Phys. Chem. C 122 3801 Google Scholar
[29]	Li H, Zhou X, Parham S, Nummy T, Griffith J, Gordon K N, Chronister E L, Dessau D S 2019 Phys. Rev. B 100 064511 Google Scholar
[30]	Neha P, Bhardwaj A, Sahu V, Patnaik S 2018 Physica C 554 1 Google Scholar
[31]	Liu W H, Lin H, Kang R Z, Zhu X Y, Zhang Y, Zheng S X, Wen H H 2017 Phys. Rev. B 96 224501 Google Scholar
[32]	Pinto N, Di Nicola C, Trapananti A, Minicucci M, Di Cicco A, Marcelli A, Bianconi A, Marchetti F, Pettinari C, Perali A 2020 Condens. Matter 5 78 Google Scholar

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芳香超导体: 电-声耦合与电子关联