57Fe M\"ossbauer study of unusual magnetic structure of multiferroic 3R-AgFeO2

TL;DR

This study uses 57Fe Mössbauer spectroscopy to investigate the complex magnetic structures of multiferroic 3R-AgFeO2 across different temperatures, revealing a transition from collinear SDW to elliptical cycloidal order influenced by exchange interactions.

Contribution

It provides detailed insights into the temperature-dependent magnetic structures of 3R-AgFeO2, highlighting the role of anisotropy and exchange topology in its multiferroic behavior.

Findings

Magnetic phase transitions at ~14 K and ~9 K identified.

Intermediate phase exhibits complex SDW with high-order harmonics.

Low-temperature phase shows elliptical cycloidal magnetic structure.

Abstract

We report new results of a 57Fe M\"ossbauer study of multiferroic 3R-AgFeO2 powder samples performed in a wide temperature range, including two points, TN1 ~ 14 K and TN2 ~ 9 K, of magnetic phase transitions. At the intermediate temperature range, TN2 < T < TN1, the 57Fe M\"ossbauer spectra can be described in terms of collinear spin-density-waves (SDW) with the inclusion of many high-order harmonics, indicating that the real magnetic structure of this ferrite appears to be more complicated than a pure sinusoidally modulated SDW. The spectra at low temperatures, T < TN2, consist of a Zeeman pattern with line broadenings and sizeable spectral asymmetry. It has been shown that the observed spectral shape is consistent with a transition to the elliptical cycloidal magnetic structure. An analysis of the experimental spectra was carried out under the assumption that the electric hyperfine interactions are modulated when the Fe3+ magnetic moment rotates with respect to the principal axis of the EFG tensor and emergence of the strong anisotropy of the magnetic hyperfine field Hhf at the 57Fe nuclei. The large and temperature-independent anharmonicity parameter, m ~ 0.78, of the cycloidal spin structure obtained from the experimental spectra results from easy-axis anisotropy in the plane of rotation of the iron spin. Analysis of different mechanisms of spin and hyperfine interactions in 3R-AgFeO2 and its structural analogue CuFeO2 points to a specific role played by the topology of the exchange coupling and the oxygen polarization in the delafossite structures.