Local Disorder in the Oxygen Environment Around Praseodymium in YBCO:Pr from X-ray Absorption Fine Structure

TL;DR

This study uses X-ray absorption spectroscopy to investigate local oxygen disorder around praseodymium in YBCO, revealing partial oxygen site disorder and mixed valence states of Pr, which impact the local structure.

Contribution

It provides detailed local structural information about Pr substitution in YBCO, highlighting oxygen disorder and mixed valence states not previously characterized.

Findings

Pr substitutes mainly on Y site with ordered structure

Reduced Pr-O peak amplitude correlates with Pr concentration

Evidence of oxygen disorder and mixed valence states around Pr

Abstract

We present K-edge XAFS (X-Ray Absorption Fine Structure) data for various concentrations of Pr in Y$_{1- x}$Pr$_{x}$Ba$_{2}$Cu$_{3}$O$_{7}$. The character of the Pr K-edge XAFS data indicate that most of the Pr substitutes onto the Y site and is well ordered with respect to the unit cell. These data also show that the amplitude of the first Pr-O peak is greatly reduced when compared to the first Y-O peak in pure YBCO, and decreases with increasing Pr concentration. In contrast, the Y K-edge data for these alloys show little if any change in the oxygen environment, while the Cu K-edge data show a 10\% reduction in the first Cu-O peak. Fits to the Pr data suggest that some oxygen atoms about the Pr become disordered and/or distorted; most of the Pr-O nearest- neighbor distances are 2.45 \AA, but about 15-40\% of them are in a possibly broadened peak at 2.27$^{+0.03}_{-0.12}$ \AA. The Cu K-edge XAFS data show a slight broadening but no loss of oxygens, which is consistent with a radial distortion of the Pr-O bond. The existence and the size of these two bond lengths is consistent with a mixture of Pr$^{3+}$ and Pr$^{4+}$ bonds, and to a formal valence of +3.33$^{+0.07}_{-0.18}$ for the Pr ion. This paper should be published in Feb. 1994 in Phys. Rev. B.