Long-range Ni/Mn structural order in epitaxial double perovskite La2NiMnO6 thin films

TL;DR

This study investigates how long-range Ni/Mn ordering in La2NiMnO6 thin films affects their structural, magnetic, and optical properties, revealing significant differences from disordered counterparts due to changes in crystal symmetry and electronic configurations.

Contribution

It provides detailed comparative analysis of ordered and disordered La2NiMnO6 films, highlighting the impact of B-site Ni/Mn ordering on their physical properties and structural signatures.

Findings

Ordered films show additional XRD reflections indicating monoclinic symmetry.

Ordered samples exhibit extra phonon excitations due to zone folding.

Ordered films have higher saturation magnetization and transition temperature.

Abstract

We report and compare the structural, magnetic, and optical properties of ordered La2NiMnO6 thin films and its disordered LaNi0.5Mn0.5O3 counterpart. An x-ray diffraction study reveals that the B-site Ni/Mn ordering induces additional XRD reflections as the crystal symmetry is transformed from a pseudocubic perovskite unit cell in the disordered phase to a monoclinic form with larger lattice parameters for the ordered phase. Polarized Raman spectroscopy studies reveal that the ordered samples are characterized by additional phonon excitations that are absent in the disordered phase. The appearance of these additional phonon excitations is interpreted as the clearest signature of Brillouin zone folding as a result of the long-range Ni/Mn ordering in La2NiMnO6. Both ordered and disordered materials display a single ferromagnetic-to-paramagnetic transition. The ordered films display also a saturation magnetization close to 4.8 mB/f.u. and a transition temperature (FM-TC) around 270 K, while the disordered ones have only a 3.7 mB/f.u. saturation magnetization and a FM-TC around 138 K. The differences in their magnetic behaviours are understood based on the distinct local electronic configurations of their Ni/Mn cations.