Klie R F, Buban J P, Varela M, Franceschetti A, Jooss C, Zhu Y, Browning N D, Pantelides S T, Pennycook S J
Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, New York 11973, USA.
Nature. 2005 May 26;435(7041):475-8. doi: 10.1038/nature03644.
Large-scale applications of high-transition-temperature (high-T(c)) superconductors, such as their use in superconducting cables, are impeded by the fact that polycrystalline materials (the only practical option) support significantly lower current densities than single crystals. The superconducting critical current density (J(c)) across a grain boundary drops exponentially if the misorientation angle exceeds 2 degrees -7 degrees. Grain texturing reduces the average misorientation angle, but problems persist. Adding impurities (such as Ca in YBa2Cu3O7-delta; YBCO) leads to increased J(c) (refs 9, 10), which is generally attributed to excess holes introduced by Ca2+ substituting for Y3+ (ref. 11). However, a comprehensive physical model for the role of grain boundaries and Ca doping has remained elusive. Here we report calculations, imaging and spectroscopy at the atomic scale that demonstrate that in poly-crystalline YBCO, highly strained grain-boundary regions contain excess O vacancies, which reduce the local hole concentration. The Ca impurities indeed substitute for Y, but in grain-boundary regions under compression and tension they also replace Ba and Cu, relieving strain and suppressing O-vacancy formation. Our results demonstrate that the ionic radii are more important than their electronic valences for enhancing J(c).
高温超导体的大规模应用,比如用于超导电缆,受到这样一个事实的阻碍:多晶材料(唯一可行的选择)所支持的电流密度比单晶材料要低得多。如果取向差角超过2度至7度,穿过晶界的超导临界电流密度(J(c))会呈指数下降。晶粒织构化减小了平均取向差角,但问题依然存在。添加杂质(如在YBa2Cu3O7-δ(YBCO)中添加Ca)会导致J(c)增加(参考文献9、10),这通常归因于Ca2+替代Y3+引入的过量空穴(参考文献11)。然而,关于晶界和Ca掺杂作用的全面物理模型仍然难以捉摸。在此,我们报告了在原子尺度上的计算、成像和光谱分析,结果表明,在多晶YBCO中,高度应变的晶界区域含有过量的氧空位,这降低了局部空穴浓度。Ca杂质确实替代了Y,但在受压和受拉的晶界区域,它们也替代了Ba和Cu,缓解了应变并抑制了氧空位的形成。我们的结果表明,对于提高J(c)而言,离子半径比它们的电子价态更重要。