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2020 Fiscal Year Research-status Report

Development of new high Tc superconductors through internal and external dual-direction doping of carbon superatoms

Research Project

Project/Area Number 18K18724
Research InstitutionOsaka Prefecture University

Principal Investigator

プラシデス コスマス  大阪府立大学, 工学(系)研究科(研究院), 教授 (90719006)

Project Period (FY) 2018-06-29 – 2022-03-31
KeywordsSuperconductivity / Molecular nanocarbons / Endohedral fullerene / Dual doping / Magnetism
Outline of Annual Research Achievements

Most superconductors have simple structures built from atoms, but superconductors made from molecules arranged in solid structures also exist.
Prominent examples are those of nanocarbon superatoms, the fullerenes (C60) - they show the highest superconducting transition temperature, Tc (38 K) and do not lose their zero resistance performance even under extremely high magnetic fields (>90 Tesla). However, they have now reached their upper limit of performance. In this research, we are attempting to remove this roadblock by using a new building block for molecular superconductors beyond the C60 nanocarbon molecule. This is [Li@C60], an endohedral metallofullerene, which incorporates a Li+ ion inside the C60- cage. We have now developed a scalable method to obtain neutral Li+@C60(-) by chemical reduction of Li+@C60 using decamethylferrocene. The preparative route does not demand long reaction times unlike electrolytic reduction routes. Investigation of solid [Li@C60] revealed the presence mainly of dimers (Li@C60)2, together with the co-existence of a small fraction of the EPR-active monomer form. These results added pieces of important information on the chemistry of the endohedral metal fulleride [Li@C60] as an emerging metal/carbon hybrid. At present, we have achieved a full structural characterization of the structural properties of the endohedral metallofullerene as a function of temperature down to liquid helium temperatures and as a function of pressure up to applied hydrostatic pressures of 12 GPa.

Current Status of Research Progress
Current Status of Research Progress

1: Research has progressed more than it was originally planned.

Reason

Superconductors have no electrical resistance and carry electricity without losing energy. The development of new materials in order to achieve
transition temperatures to zero-resistance as high as possible is at the extreme forefront of current challenges in materials science. C60
superconductors played leading role in materials research in the last 30 years achieving a robust zero-resistance state at record temperatures and surviving at extremely high magnetic fields. But they have reached their upper limit. Here we are facing the challenge of surpassing the past performance of C60 superconductors. We are targeting to achieve this by developing the uncharted field of high-symmetry superatomic carbon frameworks with metal ions inside the cages and using unprecedented mechanisms of electronic control by dual-direction internal and external electron doping. This is a challenging proposal because there are simply no systems of this type created before and, if and when made, theory predicts superb performance. Currently we have achieved the first milestone of producing and characterizing in the bulk the parent neutral lithium endohedral C60 fullerene both as a function of temperature and pressure - this constitutes the starting material, the synthon of our eventual targets and confirms that we are progressing at an excellent pace for this research.

Strategy for Future Research Activity

Our research plan follows two complementary procedures: (i) to develop the new synthetic chemistry needed, and (ii) to combine it with advanced structural and physical property measurements and feedback from theory. The research will include: [1] Synthesis of dual-direction-doped A+n[Li+@C60(n+1)-] phases (A = alkali metal; n = 1-6). This will define the full range of valences and electronic ground states in C60 cages dually-electron-doped internally and externally. [2] Physical control of structure and properties. Application of pressure will be used to drive insulator-to-metal transitions and trigger the emergence of superconductivity out of non-superconducting A+n[Li+@C60(n+1)-] precursors away from half filling of the conduction band. [3] Electronic and magnetic ground states in the new materials. The strong interplay between crystal and electronic structure requires the use of many advanced experimental techniques at both ambient and elevated pressures. We have the expertise to employ the full range of experimental techniques to investigate crystal structure (synchrotron X-ray & neutron diffraction), electronic
structure (magnetometry, transport properties, specific heat) and dynamics (NMR/muSR/EPR & IR/Raman spectroscopy) throughout the project duration. The integrated study of structure and electronic properties in the normal and superconducting states will be the basis for theoretical understanding of the new metallic/superconducting ground states.

Causes of Carryover

The original targets of this research project were rapidly achieved and we were proceeding in targeting the availability of the endohedral metallofullerene materials in large-quantities to allow full exploratory synthesis. The next steps involved more elaborate structural and physical characterization as a function of temperature as well as the utilization of high pressure to enhance the properties. Progress along these lines was severely impeded by the coronavirus pandemic. We anticipate that the significant resources necessary to proceed with the implementation, including those carried over will allow completion of the project.

  • Research Products

    (12 results)

All 2021 2020 Other

All Int'l Joint Research (4 results) Journal Article (4 results) (of which Int'l Joint Research: 4 results,  Peer Reviewed: 4 results,  Open Access: 2 results) Presentation (3 results) Remarks (1 results)

  • [Int'l Joint Research] University of Liverpool(英国)

    • Country Name
      UNITED KINGDOM
    • Counterpart Institution
      University of Liverpool
  • [Int'l Joint Research] Aristotle University of Thessaloniki(ギリシャ)

    • Country Name
      GREECE
    • Counterpart Institution
      Aristotle University of Thessaloniki
  • [Int'l Joint Research] Jozef Stefan Institute Ljubljana(スロベニア)

    • Country Name
      SLOVENIA
    • Counterpart Institution
      Jozef Stefan Institute Ljubljana
  • [Int'l Joint Research] HPSTAR Beijing(中国)

    • Country Name
      CHINA
    • Counterpart Institution
      HPSTAR Beijing
  • [Journal Article] Chemical tuning of samarium valence in mixed valence (Sm1-Ca )2.75C60 fullerides2021

    • Author(s)
      Yoshikane Naoya、Nakagawa Takeshi、Matsui Keisuke、Yamaoka Hitoshi、Hiraoka Nozomu、Ishii Hirofumi、Arvanitidis John、Prassides Kosmas
    • Journal Title

      Journal of Physics and Chemistry of Solids

      Volume: 150 Pages: 109822~109822

    • DOI

      10.1016/j.jpcs.2020.109822

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] High-pressure Raman study of the alkaline-earth metal fulleride, Ca2.75C602020

    • Author(s)
      Terzidou A. G. V.、Nakagawa T.、Yoshikane N.、Rountou R.、Rix J.、Karabinaki O.、Christofilos D.、Arvanitidis J.、Prassides K.
    • Journal Title

      Modern Physics Letters B

      Volume: 34 Pages: 2040056~2040056

    • DOI

      10.1142/S0217984920400564

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Crystal Structure and Stoichiometric Composition of Potassium-Intercalated Tetracene2020

    • Author(s)
      Hiley Craig I.、Inglis Kenneth K.、Zanella Marco、Zhang Jiliang、Manning Troy D.、Dyer Matthew S.、Knaflic Tilen、Arcon Denis、Blanc Frederic、Prassides Kosmas、Rosseinsky Matthew J.
    • Journal Title

      Inorganic Chemistry

      Volume: 59 Pages: 12545~12551

    • DOI

      10.1021/acs.inorgchem.0c01635

    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Pressure-induced valence transition in the mixed-valence (Sm1/3Ca2/3)2.75C60 fulleride2020

    • Author(s)
      Yoshikane Naoya、Matsui Keisuke、Nakagawa Takeshi、Terzidou Anastasia G. V.、Takabayashi Yasuhiro、Yamaoka Hitoshi、Hiraoka Nozomu、Ishii Hirofumi、Arvanitidis John、Prassides Kosmas
    • Journal Title

      Materials Chemistry Frontiers

      Volume: 4 Pages: 3521~3528

    • DOI

      10.1039/D0QM00707B

    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Presentation] Chemical tuning of samarium valence in mixed valence (Sm1-xCax)2.75C60 fullerides2020

    • Author(s)
      Naoya Yoshikane, Kosmas Prassides
    • Organizer
      The 2020 Autumn Meeting, The Physical Society of Japan (online)
  • [Presentation] Rare-earth valence responses to pressure in ternary rare-earth fullerides Sm2.75-xEuxC602020

    • Author(s)
      Keisuke Matsui, Kosmas Prassides
    • Organizer
      The 2020 Autumn Meeting, The Physical Society of Japan (online)
  • [Presentation] Chemical tuning of samarium valence in mixed valence (Sm1-xCax)2.75C60 Fullerides2020

    • Author(s)
      Naoya Yoshikane, Kosmas Prassides
    • Organizer
      The 70th Conference of Japan Society of Coordination Chemistry (online)
  • [Remarks] Electronic Functional Materials Laboratory

    • URL

      http://mtr1.osakafu-u.ac.jp/prassides-lab/

URL: 

Published: 2021-12-27  

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