On the strong impact of doping in the triangular antiferromagnet CuCrO2

TL;DR

This study combines electronic structure calculations and experimental characterizations to reveal how minimal Mg doping significantly influences the magnetic and transport properties of CuCrO2, a triangular antiferromagnetic semiconductor.

Contribution

It provides new insights into the limited solubility of Mg in CuCrO2 and the role of Cr^4+ holes in its transport properties, highlighting the doping's strong impact.

Findings

Mg solubility limit is very low (~1%) in CuCrO2.

Mg doping introduces Cr^4+ holes affecting transport properties.

Magnetic and electrical measurements support hole-mediated conduction.

Abstract

Electronic band structure calculations using the augmented spherical wave method have been performed for CuCrO2. For this antiferromagnetic (T_N = 24 K) semiconductor crystallizing in the delafossite structure, it is found that the valence band maximum is mainly due to the t_2g orbitals of Cr^3+ and that spin polarization is predicted with 3 mu_B per Cr^3+. The structural characterizations of CuCr1-xMgxO2 reveal a very limited range of Mg^2+ substitution for Cr^3+ in this series. As soon as x = 0.02, a maximum of 1% Cr ions substituted by Mg site is measured in the sample. This result is also consistent with the detection of Mg spinel impurities from X-ray diffraction for x = 0.01. This explains the saturation of the Mg^2+ effect upon the electrical resistivity and thermoelectric power observed for x > 0.01. Such a very weak solubility limit could also be responsible for the discrepancies found in the literature. Furthermore, the measurements made under magnetic field (magnetic susceptibility, electrical resistivity and Seebeck coefficient) support that the Cr^4+ "holes", created by the Mg^2+ substitution, in the matrix of high spin Cr^3+ (S = 3/2) are responsible for the transport properties of these compounds.