Copper K-Edge X-ray Absorption Studies of La(2)(-)(x)()K(x)()CuO(4) Superconductors, Ba(4)NaCuO(4)(CO(3))(2), and NdCu(2)O(4).
X-ray near-edge absorption spectroscopy (XANES) measurements are reported at the Cu K-edge for La(2)(-)(x)()K(x)()CuO(4) superconductors with x = 0.1 and 0.2. Comparisons of the data were made with the absorption spectra of a Cu(II) standard (La(2)CuO(4)), a new Cu(III) standard (Ba(4)NaCuO(4)(CO(3))(2)), and a new mixed-valent Cu(II)/Cu(III) phase (NdCu(2)O(4)). There is a consistent increase in the energy of the main Cu absorption edge in the following series: La(2)CuO(4) < La(1.9)K(0.1)CuO(4) < La(1.8)K(0.2)CuO(4) approximately NdCu(2)O(4) < Ba(4)NaCuO(4)(CO(3))(2). This trend can be attributed to an increase in the average Cu valence and to a decrease in bond length and an increase in covalency. The magnitude of the energy shift from Cu(II) to Cu(III) for the main absorption edge is approximately 3 eV. There is no measurable change in the energy of the pre-edge feature irrespective of Cu valence. Furthermore, no new features appear at the edge for samples with formal oxidation state between 2 and 3, even for NdCu(2)O(4), which contains both Cu(II) and Cu(III) in crystallographically distinct sites.
Stoll
Sarah L.
SL
Central Research and Development, Du Pont Company, Experimental Station, Wilmington, Delaware 19880-0356.
Bornick
Robert M.
RM
Stacy
Angelica M.
AM
VerNooy
Paul D.
PD