Bulletin of the Korean Chemical Society

Korean Chemical Society (대한화학회)
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Spectroscopic Studies on the High-$T_c$ Superconducting $La_2CuO_{4-δ}$ Prepared by Electrochemical Oxidation

  • Published : 1997.09.20
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Abstract

A superconducting phase La2CuO4+δ (Tc=44 K) has been prepared by electrochemical oxidation which allows the oxygen to intercalat into the La2O2 layers. According to the Cu K-edge X-ray absorption near edge structure spectroscopic analysis, the oxidized phase shows an overall spectra shift of about 0.5 eV to a higher energy region compared to the as sintered one with the occurrence of an additional peak corresponding to the transition to the |1s13dn+1L-14pσ1 > final state, indicating the oxidation of CuO2 layer. From the X-ray photoelectron spectroscopic studies, it is found that the binding energy of La 3d5/2 is significantly shifted from 834.3 eV (as sintered La2CuO4) to 833.6 eV (as electrochemically oxidized La2CuO4+δ), implying that the covalency of the (La-O) bond is decreased due to the oxygen intercalation. The O 1s spectra do not provide an evidence of the superoxide or peroxide, but the oxide (O2-) with the contaminated carbonate (CO32-) based on the peaks at 529 eV and 532 eV, respectively, which is clearly confirmed by the Auger spectroscopic analysis. Oxygen contents determined by iodometric titration (δ=0.07) and thermogravimetry (δ=0.09) show good coincidence each other, also giving an evidence for the "O2-" nature of excess oxygen. From the above results, it is concluded that "O2-" appeared as O 1s peak at 528.6 eV is responsible for superconductivity of La2CuO4+δ.

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