Park J C, Kim D K, Byeon S H, Kim D
Department of Chemistry of New Materials, College of Natural Sciences, Silla University, Pusan, Korea.
J Synchrotron Radiat. 2001 Mar 1;8(Pt 2):704-6. doi: 10.1107/s0909049500015983.
Ruddlesden-Popper phase, La(n+1)Ni(n)O(3n+1 (n=1, 2, and infinity) compounds were prepared by citrate sol-gel method. We revealed the origin of the variation of the electrical conductivities in La(n+1)Ni(n)O(3n+1 (n=1, 2, and infinity) using resistivity measurements, Rietveld analysis, and X-ray absorption spectroscopy. According to the XANES spectra, it is found that the degree of 4p(pi) - 4psigma energy splitting between 8345 eV and 8350 eV is qualitatively proportional to the elongation of the out-of-plane Ni-O bond length. With the decrease of 4p(pi) - 4psigma splitting, the strong hybridization of the sigma-bonding between Ni-3d and O-2p orbitals creates narrow antibonding sigma* bands, which finally results in the lower electrical resistivity.
通过柠檬酸盐溶胶-凝胶法制备了Ruddlesden-Popper相的La(n+1)Ni(n)O(3n+1)(n = 1、2和无穷大)化合物。我们使用电阻率测量、Rietveld分析和X射线吸收光谱揭示了La(n+1)Ni(n)O(3n+1)(n = 1、2和无穷大)中电导率变化的起源。根据XANES光谱,发现在8345 eV和8350 eV之间4p(π) - 4pσ能量分裂的程度与面外Ni - O键长的伸长在定性上成正比。随着4p(π) - 4pσ分裂的减小,Ni - 3d和O - 2p轨道之间σ键的强杂化产生了狭窄的反键σ*带,最终导致较低的电阻率。