Reuse & Permissions

It is not necessary to obtain permission to reuse this article or its components as it is available under the terms of the Creative Commons Attribution 4.0 International license. This license permits unrestricted use, distribution, and reproduction in any medium, provided attribution to the author(s) and the published article's title, journal citation, and DOI are maintained. Please note that some figures may have been included with permission from other third parties. It is your responsibility to obtain the proper permission from the rights holder directly for these figures.

Export citation

Export citation

Choose format for download:

Download Citation
  • Letter
  • Open Access

Thermodynamic properties of mixed-valent Eu ions and nonmetallicity in Eu3Bi2S4F4 single crystals

Ryuji Higashinaka*, Hideaki Endo, Joe Kajitani, Ryotaro Sakatani, Tatsuma D. Matsuda, and Yuji Aoki†

  • Department of Physics, Tokyo Metropolitan University, Hachioji, Tokyo 192-0397, Japan

  • *higashin@tmu.ac.jp
  • †aoki@tmu.ac.jp

Phys. Rev. B 108, L081122 – Published 25 August, 2023

DOI: https://doi.org/10.1103/PhysRevB.108.L081122

Abstract

New BiS2-based layered compound Eu3Bi2S4F4 has recently been reported to exhibit superconductivity with a transition temperature of 1.5 K using polycrystalline samples. Here we report measurements of electrical resistivity ρ, magnetization M, and specific heat C of Eu3Bi2S4F4 single crystals. At the antiferromagnetic transition temperature of 2.17 K, C(T) shows a sharp λ-type peak, suggesting the existence of strong Eu magnetic moment fluctuations due to the quasi-two-dimensional nature of the Eu-ion lattice in Eu3F4 block layers. The average Eu-ion valence of +2.19, determined from the Schottky-type 4f-electron contribution to C(T) and M(T,H), indicates the self-doped electron density in BiS2 layers due to the Eu mixed valence to be 0.285 electrons per Bi site. It has been revealed, however, that ρ(T) shows an anomalous nonmetallic behavior with ∼1/T3 dependence without any sign of superconductivity, in marked contrast to a metallic behavior in the polycrystals. This behavior suggests an unconventional electron-localization mechanism working in the single crystals, possibly caused by Eu2+/Eu3+ distribution (or fluctuations) and/or lattice instabilities inherent to BiS2 layers.

View figure in article

Physics Subject Headings (PhySH)

Article Text

Supplemental Material

References (50)

  1. Y. Mizuguchi, H. Fujihisa, Y. Gotoh, K. Suzuki, H. Usui, K. Kuroki, S. Demura, Y. Takano, H. Izawa, and O. Miura, BiS2-based layered superconductor Bi4O4S3, Phys. Rev. B 86, 220510(R) (2012).
  2. Y. Mizuguchi, S. Demura, K. Deguchi, Y. Takano, H. Fujihisa, Y. Gotoh, H. Izawa, and O. Miura, Superconductivity in novel BiS2-based layered superconductor LaO1−xFxBiS2, J. Phys. Soc. Jpn. 81, 114725 (2012).
  3. D. Yazici, I. Jeon, B. D. White, and M. B. Maple, Superconductivity in layered BiS2-based compounds, Physica C 514, 218 (2015).
  4. Y. Mizuguchi, Review of superconductivity in BiS2-based layered materials, J. Phys. Chem. Solids 84, 34 (2015).
  5. J. G. Bednorz and K. A. Muller, Possible highTc superconductivity in the Ba-La-Cu-O system, Z. Phys. B 64, 189 (1986).
  6. Y. Kamihara, T. Watanabe, M. Hirano, and H. Hosono, Iron-based layered superconductor LaO1−xFxFeAs (x=0.05−0.12) with Tc=26 K, J. Am. Chem. Soc. 130, 3296 (2008).
  7. D. Yazici, K. Huang, B. D. White, I. Jeon, V. W. Burnett, A. J. Friedman, I. K. Lum, M. Nallaiyan, S. Spagna, and M. B. Maple, Superconductivity induced by electron doping in La1−xMxOBiS2 (M=Ti, Zr, Hf, Th), Phys. Rev. B 87, 174512 (2013).
  8. H. Sakai, D. Kotajima, K. Saito, H. Wadati, Y. Wakisaka, M. Mizumaki, K. Nitta, Y. Tokura, and S. Ishiwata, Insulator-to-superconductor transition upon electron doping in a BiS2-based superconductor Sr1−xLaxFBiS2, J. Phys. Soc. Jpn. 83, 014709 (2014).
  9. H. Usui, K. Suzuki, and K. Kuroki, Minimal electronic models for superconducting BiS2 layers, Phys. Rev. B 86, 220501(R) (2012).
  10. T. Sugimoto, D. Ootsuki, C. Morice, E. Artacho, S. S. Saxena, E. F. Schwier, M. Zheng, Y. Kojima, H. Iwasawa, K. Shimada, M. Arita, H. Namatame, M. Taniguchi, M. Takahashi, N. L. Saini, T. Asano, R. Higashinaka, T. D. Matsuda, Y. Aoki, and T. Mizokawa, Fermi surfaces and orbital polarization in superconducting CeO0.5F0.5BiS2 revealed by angle-resolved photoemission spectroscopy, Phys. Rev. B 92, 041113(R) (2015).
  11. Z. R. Ye, H. F. Yang, D. W. Shen, J. Jiang, X. H. Niu, D. L. Feng, Y. P. Du, X. G. Wan, J. Z. Liu, X. Y. Zhu, H. H. Wen, and M. H. Jiang, Electronic structure of single-crystalline NdO0.5F0.5BiS2 studied by angle-resolved photoemission spectroscopy, Phys. Rev. B 90, 045116 (2014).
  12. M. Nagao, A. Miura, S. Demura, K. Deguchi, S. Watauchi, T. Takei, Y. Takano, N. Kumada, and I. Tanaka, Growth and superconducting properties of F-substituted ROBiS2 (R = La, Ce, Nd) single crystals, Solid State Commun. 178, 33 (2014).
  13. M. Nagao, M. Tanaka, S. Watauchi, I. Tanaka, and Y. Takano, Superconducting anisotropies of F-substituted LaOBiSe2 single crystals, J. Phys. Soc. Jpn. 83, 114709 (2014).
  14. R. Higashinaka, T. Asano, T. Nakashima, K. Fushiya, Y. Mizuguchi, O. Miura, T. D. Matsuda, and Y. Aoki, Pronounced -LogT divergence in specific heat of nonmetallic CeOBiS2: A mother phase of BiS2-based superconductor, J. Phys. Soc. Jpn. 84, 023702 (2015).
  15. T. Sugimoto, D. Ootsuki, E. Paris, A. Iadecola, M. Salome, E. F. Schwier, H. Iwasawa, K. Shimada, T. Asano, R. Higashinaka, T. D. Matsuda, Y. Aoki, N. L. Saini, and T. Mizokawa, Localized and mixed valence state of Ce 4f in superconducting and ferromagnetic CeO1−xFxBiS2 revealed by x-ray absorption and photoemission spectroscopy, Phys. Rev. B 94, 081106(R) (2016).
  16. T. Sugimoto, E. Paris, T. Wakita, K. Terashima, T. Yokoya, A. Barinov, J. Kajitani, R. Higashinaka, T. D. Matsuda, Y. Aoki, T. Mizokawa, and N. L. Saini, Metallic phase in stoichiometric CeOBiS2 revealed by space-resolved ARPES, Sci. Rep. 8, 2011 (2018).
  17. A. Miura, M. Nagao, Y. Goto, Y. Mizuguchi, T. D. Matsuda, Y. Aoki, C. Moriyoshi, Y. Kuroiwa, Y. Takano, S. Watauchi, I. Tanaka, N. C. Rosero-Navarro, and K. Tadanaga, Crystal structure and superconductivity of tetragonal and monoclinic Ce1−xPrxOBiS2, Inorg. Chem. 57, 5364 (2018).
  18. H. F. Zhai, Z. T. Tang, H. Jiang, K. Xu, K. Zhang, P. Zhang, J. K. Bao, Y. L. Sun, W. H. Jiao, I. Nowik, I. Felner, Y. K. Li, X. F. Xu, Q. Tao, C. M. Feng, Z. A. Xu, and G. H. Cao, Possible charge-density wave, superconductivity, and f-electron valence instability in EuBiS2F, Phys. Rev. B 90, 064518 (2014).
  19. H. F. Zhai, P. Zhang, and G. H. Cao, Superconductivity in europium bismuth sulfofluorides, J. Phys. Soc. Jpn. 88, 041003 (2019).
  20. T. Sugimoto, E. Paris, K. Terashima, A. Barinov, A. Giampietri, T. Wakita, T. Yokoya, J. Kajitani, R. Higashinaka, T. D. Matsuda, Y. Aoki, T. Mizokawa, and N. L. Saini, Inhomogeneous charge distribution in a self-doped EuFBiS2 superconductor, Phys. Rev. B 100, 064520 (2019).
  21. S. Demura, Ordered states coexisting with superconductivity in BiCh2 materials, J. Phys. Soc. Jpn. 88, 041002 (2019).
  22. J. Xing, S. Li, X. Ding, H. Yang, and H.-H. Wen, Superconductivity appears in the vicinity of semiconducting-like behavior in CeO1−xFxBiS2, Phys. Rev. B 86, 214518 (2012).
  23. S. Demura, K. Deguchi, Y. Mizuguchi, K. Sato, R. Honjyo, A. Yamashita, T. Yamaki, H. Hara, T. Watanabe, S. J. Denholme, M. Fujioka, H. Okazaki, T. Ozaki, O. Miura, T. Yamaguchi, H. Takeya, and Y. Takano, Coexistence of bulk superconductivity and magnetism in CeO1−xFxBiS2, J. Phys. Soc. Jpn. 84, 024709 (2015).
  24. R. Jha and V. P. S. Awana, Superconductivity in layered CeO0.5F0.5BiS2, J. Supercond. Novel Magn. 27, 1 (2014).
  25. H. F. Zhai, P. Zhang, S. Q. Wu, C. Y. He, Z. Tu. Tang, H. Jiang, Y. L. Sun, J. K. Bao, I. Nowik, I. Felner, Y. W. Zeng, Y. K. Li, X. F. Xu, Q. Tao, Z. A. Xu, and G. H. Cao, Anomalous Eu valence state and superconductivity in undoped Eu3Bi2S4F4, J. Am. Chem. Soc. 136, 15386 (2014).
  26. K. Ishigaki, J. Gouchi, K. Torizuka, S. Arumugam, A. K. Ganguli, G. Kalaiselvan, Z. Haque, G. S. Thakur, L. C. Gupta, and Y. Uwatoko, Pressure effect on the BiS2 layered compound Eu3Bi2S4F4, JPS Conf. Proc. 30, 011058 (2020).
  27. Y. Luo, H. F. Zhai, P. Zhang, Z. A. Xu, G. H. Cao, and J. D. Thompson, Pressure-enhanced superconductivity in Eu3Bi2S4F4, Phys. Rev. B 90, 220510(R) (2014).
  28. P. Zhang, H. F. Zhai, Z. J. Tang, L. Li, Y. K. Li, Q. Chen, J. Chen, Z. Wang, C. M. Feng, G. H. Cao, and Z. A. Xu, Superconductivity enhanced by Se doping in Eu3Bi2(S,Se)4F4, Europhys. Lett. 111, 27002 (2015).
  29. Z. Haque, G. S. Thakur, R. Parthasarathy, B. Gerke, T. Block, L. Heletta, R. Pöttgen, A. G. Joshi, G. K. Selvan, S. Arumugam, L. C. Gupta, and A. K. Ganguli, Unusual mixed valence of Eu in two materials–EuSr2Bi2S4F4 and Eu2SrBi2S4F4: Mössbauer and x-ray photoemission spectroscopy investigations, Inorg. Chem. 56, 3182 (2017).
  30. Z. Haque, G. S. Thakur, G. K. Selvan, T. Block, O. Janka, R. Pöttgen, A. G. Joshi, R. Parthasarathy, S. Arumugam, L. C. Gupta, and A. K. Ganguli, Valence state of Eu and superconductivity in se-substituted EuSr2Bi2S4F4 and Eu2SrBi2S4F4, Inorg. Chem. 57, 37 (2018).
  31. P. Zhang, H. F. Zhai, Z. Wang, J. Chen, C. M. Feng, G. H. Cao, and Z. A. Xu, Effect of Sr doping in layered Eu3Bi2S4F4 superconductor, Supercond. Sci. Technol. 30, 015005 (2017).
  32. M. Nagao, Growth and characterization of R(O, F)BiS2 (R = La, Ce, Pr, Nd) superconducting single crystals, Nov. Supercond. Mater. 1, 64 (2015).
  33. M. Nagao, M. Tanaka, S. Watauchi, Y. Takano, and I. Tanaka, Growth and superconducting properties of Cd-doped La(O, F)BiS2 single crystals, Solid State Commun. 261, 32 (2017).
  34. Y. C. Chan, K. Y. Yip, Y. W. Cheung, Y. T. Chan, Q. Niu, J. Kajitani, R. Higashinaka, T. D. Matsuda, Y. Yanase, Y. Aoki, K. T. Lai, and S. K. Goh, Anisotropic two-gap superconductivity and the absence of a Pauli paramagnetic limit in single-crystalline LaO0.5F0.5BiS2, Phys. Rev. B 97, 104509 (2018).
  35. F. Giubileo, F. Romeo, A. Di Bartolomeo, Y. Mizuguchi, and P. Romano, Probing unconventional pairing in LaO0.5F0.5BiS2 layered superconductor by point contact spectroscopy, J. Phys. Chem. Solids 118, 192 (2018).
  36. R. Higashinaka, H. Endo, J. Kajitani, T. D. Matsuda, and Y. Aoki, Single crystal growth and physical properties of BiS2-layered compound Eu3Bi2S4F4, Phys. B: Condens. Matter 536, 824 (2018).
  37. See Supplemental Material at http://link.aps.org/supplemental/10.1103/PhysRevB.108.L081122 for the characterization of single crystals, the Van Vleck paramagnetic susceptibility for a free Eu3+ ion,the specific heat data analyses, and a concave upward curvature of the [001] magnetization curves. It also contains Refs. [38, 39].
  38. J. H. Van Vleck, in The Theory of Electric and Magnetic Susceptibilities (Oxford University Press, Oxford, 1932), p. 226.
  39. B. Bleaney, Hyperfine Interactions in rare-earth metals, J. Appl. Phys. 34, 1024 (1963).
  40. E. Paris, T. Sugimoto, T. Wakita, A. Barinov, K. Terashima, V. Kandyba, O. Proux, J. Kajitani, R. Higashinaka, T. D. Matsuda, Y. Aoki, T. Yokoya, T. Mizokawa, and N. L. Saini, Electronic structure of self-doped layered Eu3F4Bi2S4 material revealed by x-ray absorption spectroscopy and photoelectron spectromicroscopy, Phys. Rev. B 95, 035152 (2017).
  41. Y. Takikawa, S. Ebisu, and S. Nagata, Van Vleck paramagnetism of the trivalent Eu ions, J. Phys. Chem. Solids 71, 1592 (2010).
  42. Y. Aoki, H. R. Sato, H. Sugawara, and H. Sato, Anomalous magnetic properties of Heusler superconductor YbPd2Sn, Physica C: Superconduct. 333, 187 (2000).
  43. P. A. Lee and T. V. Ramakrishnan, Disordered electronic systems, Rev. Mod. Phys. 57, 287 (1985).
  44. N. F. Mott, Metal-Insulator Transitions (Taylor & Francis, London, 1974).
  45. T. Yildirim, Ferroelectric soft phonons, charge density wave instability, and strong electron-phonon coupling in BiS2 layered superconductors: A first-principles study, Phys. Rev. B 87, 020506(R) (2013).
  46. R. Sagayama, H. Sagayama, R. Kumai, Y. Murakami, T. Asano, J. Kajitani, R. Higashinaka, T. D. Matsuda, and Y. Aoki, Symmetry lowering in LaOBiS2: A mother material for BiS2-based layered superconductors, J. Phys. Soc. Jpn. 84, 123703 (2015).
  47. J. Kajitani, R. Sagayama, H. Sagayama, K. Matsuura, T. Hasegawa, R. Kumai, Y. Murakami, M. Mita, T. Asano, R. Higashinaka, T. D. Matsuda, and Y. Aoki, Transverse-type lattice modulation in LaO0.5F0.5BiS2: Possible charge density wave formation, J. Phys. Soc. Jpn. 90, 103601 (2021).
  48. H. Tamatsukuri, T. Hasegawa, H. Sagayama, M. Mizumaki, Y. Murakami, J. Kajitani, R. Higashinaka, T. D. Matsuda, Y. Aoki, and S. Tsutsui, Investigation of the phonon dispersion associated with superlattice reflections in the BiS2-based superconductor LaBiS2O0.5F0.5, Phys. Rev. B 107, 024303 (2023).
  49. J. Lee, M. Nagao, Y. Mizuguchi, and J. Ruff, Direct observation of an incommensurate charge density wave in the BiS2-based superconductor NdO1−xFxBiS2, Phys. Rev. B 103, 245120 (2021).
  50. X. Zhang, Q. Liu, J.-W. Luo, A. J. Freeman, and A. Zunger, Hidden spin polarization in inversion-symmetric bulk crystals, Nat. Phys. 10, 387 (2014).

Outline

Information

Sign In to Your Journals Account

Filter

Filter

Article Lookup

Enter a citation