Role of Ni substitution on structural, magnetic and electronic properties of epitaxial CoCr2O4 spinel thin films

TL;DR

This study investigates how Ni substitution affects the structural, magnetic, and electronic properties of epitaxial CoCr2O4 spinel thin films, revealing enhanced transition temperatures and changes in oxidation states and surface morphology.

Contribution

It provides new insights into the effects of Ni substitution on thin film properties of CoCr2O4, which were previously less explored in epitaxial form.

Findings

Ni substitution increases ferrimagnetic transition temperatures.

XPS confirms Cr3+ and mixed Co2+/Co3+ oxidation states.

Surface morphology and Raman modes are altered by Ni content.

Abstract

Cubic spinel CoCr2O4 has attained recent attention due to its multiferroic properties. However, the Co site substitution effect on the structural and magnetic properties has rarely been studied in thin film form. In this work, the structural and magnetic properties of Co1-xNixCr2O4 (x = 0, 0.5) epitaxial thin films deposited on MgAl2O4 (100) and MgO (100) substrates to manipulate the nature of strain in the films using pulsed laser deposition (PLD) technique are presented. The epitaxial nature of the films was confirmed through X-ray diffraction (XRD) and Rutherford backscattering spectrometry (RBS) measurements. Raman measurements revealed a disappearance of characteristic A1g and F2g modes of the CoCr2O4 with increase in the Ni content. Atomic force microscopy (AFM) studies show a modification of the surface morphology upon Ni substitution. Magnetic measurements disclose that the ferrimagnetic Curie temperature (Tc) of the CoCr2O4 in thin film grown on MgAl2O4 (100) and MgO (100) substrates were found to be 100.6 +/- 0.5 K and 93.8 +/- 0.2 K, respectively. With Ni substitution the transition temperatures significantly get enhanced from that of CoCr2O4. X-ray photoelectron spectroscopy (XPS) suggests Cr3+ oxidation states in the films, while Co ions are present in a mixed Co2+/Co3+ oxidation state. The substitution of Ni at Co site significantly modifies the line shape of the core level as well as the valence band. Ni ions are also found to be in a mixed 2+/3+ oxidation state. O 1s core level display asymmetry related to possible defects like oxygen vacancies in the films.