Size-Effect Enriched Phase Diagram in <i>p</i>-Type Skutterudite Superconductor Ir<sub>3.8</sub>Sb<sub>12</sub>

Pressurized Ir<sub>4</sub>X<sub>12</sub> (X = P and As) stands out as the sole <i>p</i>-type superconductors among dozens of filled-skutterudites that are primarily characterized by <i>n</i>-type charge carriers. The emergence of superconductivity is proposed to be intimately related to the inharmonic rattling phonons originating from the filled atoms. Here, we explore the impact of the size effect of the rattling atoms by substituting X with Sb, whose radius is 30 and 17% larger than those of P and As, respectively. <i>In situ</i> synchrotron X-ray diffractions reveal a similar structural evolution of self-inserted Sb atoms inside the Sb<sub>11</sub> cage but at a significantly lower critical pressure of 33.6 GPa. Interestingly, single crystalline Ir<sub>3.8</sub>Sb<sub>12</sub> exhibits a more diverse electronic phase diagram compared to its P- and As-based counterparts, encompassing an anomalous resistance upturn, a complete superconducting dome, and a filled-semiconducting region. We propose that the intrinsic deficiency of Ir and the filling ratio of central atoms, both stemming from the size effect of Sb, are responsible for the observed rich phenomena.

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Journal
Inorganic Chemistry
Published
2025-01-29
DOI
https://doi.org/10.1021/acs.inorgchem.4c04253
Primary Topic
Rare-earth and actinide compounds
Type
article
Field-Weighted Citation Impact
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article

Size-Effect Enriched Phase Diagram in p-Type Skutterudite Superconductor Ir3.8Sb12

Tianping Ying, Cuiying Pei, Jiangang Guo, Yanpeng Qi et al.
Inorganic Chemistry
Rare-earth and actinide compounds
article

Size-Effect Enriched Phase Diagram in p-Type Skutterudite Superconductor Ir3.8Sb12

Tianping Ying, Cuiying Pei, Jiangang Guo, Yanpeng Qi, Xu Liu, Junjie Wang
article en

Abstract

Pressurized Ir<sub>4</sub>X<sub>12</sub> (X = P and As) stands out as the sole <i>p</i>-type superconductors among dozens of filled-skutterudites that are primarily characterized by <i>n</i>-type charge carriers. The emergence of superconductivity is proposed to be intimately related to the inharmonic rattling phonons originating from the filled atoms. Here, we explore the impact of the size effect of the rattling atoms by substituting X with Sb, whose radius is 30 and 17% larger than those of P and As, respectively. <i>In situ</i> synchrotron X-ray diffractions reveal a similar structural evolution of self-inserted Sb atoms inside the Sb<sub>11</sub> cage but at a significantly lower critical pressure of 33.6 GPa. Interestingly, single crystalline Ir<sub>3.8</sub>Sb<sub>12</sub> exhibits a more diverse electronic phase diagram compared to its P- and As-based counterparts, encompassing an anomalous resistance upturn, a complete superconducting dome, and a filled-semiconducting region. We propose that the intrinsic deficiency of Ir and the filling ratio of central atoms, both stemming from the size effect of Sb, are responsible for the observed rich phenomena.

Inorganic ChemistryVol. 64(5)
Chinese Academy of Sciences (CN), ShanghaiTech University (CN), FZU ‒ Institute of Physics of the Academy of Sciences of the Czech Republic (CZ), Institute of Physics (CN), University of Chinese Academy of Sciences (CN)
National Natural Science Foundation of China, Chinese Academy of Sciences, Beijing Municipal Natural Science Foundation, National Key Research and Development Program of China
Openalex Percentile: Top 99%
Rare-earth and actinide compounds
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