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NaRhO晶体(0.25≤x≤1)的制备、结构演变及金属-绝缘体转变

Preparation, Structure Evolution, and Metal-Insulator Transition of Na RhO Crystals (0.25 ≤ x ≤ 1).

作者信息

Zhang Bin-Bin, Wang Cong, Dong Song-Tao, Lv Yang-Yang, Zhang Lunyong, Xu Yadong, Chen Y B, Zhou Jian, Yao Shu-Hua, Chen Yan-Feng

机构信息

National Laboratory of Solid State Microstructures Department of Materials Science and Engineering , Nanjing University , Nanjing 210093 , People's Republic of China.

Key Laboratory of Radiation Detection Materials and Devices, Ministry of Industry and Information Technology, School of Materials Science and Engineering State Key Laboratory of Solidification Processing , Northwestern Polytechnical University , Xi'an , Shaanxi 710072 , People's Republic of China.

出版信息

Inorg Chem. 2018 Mar 5;57(5):2730-2735. doi: 10.1021/acs.inorgchem.7b03110. Epub 2018 Feb 15.

Abstract

The triangular lattice Na RhO contains a 4d Rh element with large spin-orbit coupling, and the electron-electron correlation effect is expected to have some novel physical properties. Here we report NaRhO crystal growth by NaCO vapor growth and a series of Na RhO (0.25 ≤ x ≤ 1) crystals prepared using the chemical desodiation method. Na RhO reveals a layer structure with the space group R3̅ m, and the lattice parameter a evolves from 3.09 to 3.03 Å and c from 15.54 to 15.62 Å when x decreases from 1.0 to 0.2. Decreasing potassium concentration leads to a contraction of the RhO octahedral layers, which may be attributed to a higher covalency of Rh-O bonds. More important, the metal-insulator transition in Na RhO was observed in resistivity along the ab plane. The conducting mechanism of Na RhO is strongly dependent on x. Two-dimensional variable range hopping (VRH) mechanisms (0.67 ≤ x ≤ 1) and metallic behaviors (0.42 and 0.47) are observed in temperature-dependent resistivity. The origin of this metal-insulator transition was discussed on the basis of the Ioffe-Regel criterion. Our work demonstrates the strong correlation between sodium concentration and physical properties of Na RhO.

摘要

三角晶格NaRhO包含具有大自旋轨道耦合的4d铑元素,并且电子-电子关联效应预计会具有一些新颖的物理性质。在此,我们报道了通过NaCO气相生长法生长的NaRhO晶体以及使用化学脱钠法制备的一系列NaRhOₓ(0.25≤x≤1)晶体。NaRhOₓ呈现出空间群为R3̅m的层状结构,当x从1.0降至0.2时,晶格参数a从3.09 Å演变为3.03 Å,c从15.54 Å演变为15.62 Å。钾浓度的降低导致RhO八面体层收缩,这可能归因于Rh - O键更高的共价性。更重要的是,在沿ab平面的电阻率中观察到了NaRhOₓ中的金属-绝缘体转变。NaRhOₓ的导电机制强烈依赖于x。在与温度相关的电阻率中观察到了二维变程跳跃(VRH)机制(0.67≤x≤1)和金属行为(x = 0.42和0.47)。基于伊夫 - 雷格尔准则讨论了这种金属-绝缘体转变的起源。我们的工作证明了钠浓度与NaRhOₓ物理性质之间的强相关性。

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