Oxygen and Strontium Codoping of La2NiO4: Room Temperature Phase Diagrams

TL;DR

This study investigates how oxygen and strontium doping affect the phase diagrams of La2NiO4, revealing doping-dependent phase stability, suppression of phase separation at high Sr levels, and anisotropic chemical pressure effects.

Contribution

It provides detailed room temperature phase diagrams for La2-xSrxNiO4+d with combined oxygen and Sr doping, highlighting the effects on phase stability and lattice parameters.

Findings

Sr doping suppresses phase separation at high levels.

Lattice parameters depend on dopant type rather than net hole content.

Oxygen interstitials induce more isotropic chemical pressure.

Abstract

We present a detailed room temperature x-ray powder diffraction study on La2-xSrxNiO4+d with 0<=x<=0.12 and 0<=d<=0.13. For x=0.02, 0.04 and 0.06 the oxygen content phase diagrams of the Sr doped samples show a similar sequence of pure phases and miscibility gaps as for pure La2NiO4+d. We find a weak Sr doping dependence of the d-range for the pure LTO, LTT and HTT phases; but overall, the d-ranges of the different phases do not vary strongly for x<=0.06. Drastic changes are observed for x=0.08 and 0.12, where miscibility gaps successively disappear. For x=0.12 all oxygen doped samples are in the HTT phase. The mechanism responsible for the suppression of the phase separation seems to involves multiple factors, including the Coulomb interaction between Sr impurities and interstitial oxygens as well as the reduction of the NiO6 octahedral tilt angle. The doping dependence of the lattice parameters shows clear differences for pure Sr and pure O doping. With the exception of the LTO phase, the in-plane lattice parameters explicitly depend on the type of dopant, rather than the net hole content, p=x+2d. In contrast, the orthorhombic strain in the LTO phase as well as the c-axis length appears to depend only on p; however, in the case of the c-axis length this ''universal'' behavior turns out to be accidental. Our results also show that the chemical pressure of La-site dopants is highly anisotropic, whereas that of O interstitials appears to be more isotropic. In general, this study reveals that Sr-doped samples have to be annealed carefully to achieve d=0, and to permit the study of the intrinsic properties of La2-xSrxNiO4.