A-Site and B-Site Charge Orderings in an s-d Level Controlled Perovskite Oxide PbCoO3
A-Site and B-Site Charge Orderings in an s-d Level Controlled Perovskite Oxide PbCoO3
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s-d 水平控制的钙钛矿氧化物 PbCoO3 中的 A 位和 B 位电荷排序
DOI：
10.1021/jacs.7b01851
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发表时间：
2017-03-29
影响因子：
15
通讯作者：
Azuma, Masaki
中科院分区：
文献类型：
--
作者：
Sakai, Yuki;Yang, Junye;Azuma, Masaki
在12 GPa下合成的PbCoO3具有Pb（2+）Pb（3）（4+）Co（2+）2Co（2）（3+）O（12）的特殊电荷分布，在ABO（3）的A位和B位都有电荷有序化。利用密度泛函理论（DFT）计算、电子衍射（艾德）、同步辐射X射线衍射（SXRD）、中子粉末衍射（NPD）、硬X射线光电子能谱（HAXPES）、软X射线吸收谱（XAS）、比热以及磁和电性能的测量提供了铅离子和钴离子电荷有序的证据，导致Pb 2 + Pb 34 + Co 22 + Co23+O12四重钙钛矿结构。结果表明，通过调节Pb 6s轨道和过渡金属3d轨道的能级，可以稳定Pb 3.5 + Co 2.5 +O3在Pb 3 + Cr 3 +O3和Pb 4 + Ni 2 +O3之间的平均价态分布。
Perovskite PbCoO3 synthesized at 12 GPa was found to have an unusual charge distribution of Pb(2+)Pb(3)(4+)Co(2+)2Co(2)(3+)O(12) with charge orderings in both the A and B sites of perovskite ABO(3). Comprehensive studies using density functional theory (DFT) calculation, electron diffraction (ED), synchrotron X-ray diffraction (SXRD), neutron powder diffraction (NPD), hard X-ray photoemission spectroscopy (HAXPES), soft X-ray absorption spectroscopy (XAS), and measurements of specific heat as well as magnetic and electrical properties provide evidence of lead ion and cobalt ion charge ordering leading to Pb2+Pb34+Co22+Co23+O12 quadruple perovskite structure. It is shown that the average valence distribution of Pb3.5+Co2.5+O3 between Pb3+Cr3+O3 and Pb4+Ni2+O3 can be stabilized by tuning the energy levels of Pb 6s and transition metal 3d orbitals.