Department of Complex Matter, Jozef Stefan Institute, 1000 Ljubljana, Slovenia;
Department of Chemistry, Washington State University, Pullman, WA 99164.
Proc Natl Acad Sci U S A. 2020 Mar 3;117(9):4559-4564. doi: 10.1073/pnas.1918704117. Epub 2020 Feb 18.
A common characteristic of many "overdoped" cuprates prepared with high-pressure oxygen is values ≥ 50 K that often exceed that of optimally doped parent compounds, despite O stoichiometries that place the materials at the edge or outside of the conventional boundary between superconducting and normal Fermi liquid states. X-ray absorption fine-structure (XAFS) measurements at 52 K on samples of high-pressure oxygen (HPO) YSrCuMoO, = 84 K show that the Mo is in the (VI) valence in an unusually undistorted octahedral geometry with predominantly Mo neighbors that is consistent with its assigned substitution for Cu in the chain sites of the structure. Perturbations of the Cu environments are minimal, although the Cu X-ray absorption near-edge structure (XANES) differs from that in other cuprates. The primary deviation from the crystal structure is therefore nanophase separation into Mo- and Cu-enriched domains. There are, however, indications that the dynamical attributes of the structure are altered relative to YBaCuO, including a shift of the Cu-apical O two-site distribution from the chain to the plane Cu sites. Another effect that would influence is the possibility of multiple bands at the Fermi surface caused by the presence of the second phase and the lowering of the Fermi level.
许多采用高压氧制备的“过掺杂”铜酸盐的一个共同特点是 值≥50K,尽管 O 化学计量比使材料处于超导和正常费米液体状态之间的传统边界的边缘或外部,但 值往往超过最佳掺杂母体化合物的值。在 52K 下对高压氧(HPO)YSrCuMoO 的 X 射线吸收精细结构(XAFS)测量表明,Mo 处于(VI)价态,在异常未畸变的八面体几何形状中,主要是 Mo 近邻,这与其在结构链位取代 Cu 一致。Cu 环境的扰动最小,尽管 Cu 的 X 射线吸收近边结构(XANES)与其他铜酸盐不同。因此,主要的偏离是纳米相分离成 Mo 和 Cu 富集区。然而,有迹象表明,与 YBaCuO 相比,结构的动力学属性发生了变化,包括 Cu-顶端 O 双位点分布从链位到平面 Cu 位的转移。另一个会影响 值的因素是费米面可能存在第二相和费米能级降低导致的多能带。