Large Miscibility Gap in the Ba(Mn_xFe_{1-x})2As2 System

TL;DR

This study reveals a large miscibility gap in the Ba(Mn_xFe_{1-x})2As2 system, showing phase separation and a significant homogeneity range in the 122-type phase at various temperatures, with detailed structural and physical property analyses.

Contribution

It provides the first detailed characterization of the miscibility gap and phase behavior in the Ba(Mn_xFe_{1-x})2As2 system, including temperature-dependent phase boundaries and impurity phases.

Findings

Large miscibility gap at 300 K with 0.12 < x < 1

Narrowing of the miscibility gap at 1000 C to 0.2 < x < 0.8

Presence of impurity phases in quenched samples

Abstract

The compounds BaMn2As2 and BaFe2As2 both crystallize in the body-centered-tetragonal ThCr2Si2-type (122-type) structure at room temperature but exhibit quite different unit cell volumes and very different magnetic and electronic transport properties. Evidently reflecting these disparities, we have discovered a large miscibility gap in the system Ba(Mn_xFe_{1-x})2As2. Rietveld refinements of powder x-ray diffraction (XRD) measurements on samples slow-cooled from 1000 C to room temperature (RT) reveal a two-phase mixture of BaMn2As2 and Ba(Mn_{0.12}Fe_{0.88})2As2 phases together with impurity phases for x = 0.2, 0.4, 0.5, 0.6 and 0.8. We infer that there exists a miscibility gap in this system at 300 K with composition limits 0.12 < x < 1. For samples quenched from 1000 C to 77 K, the refinements of RT XRD data indicate that the miscibility gap at RT narrows at 1000 C to 0.2 < x < 0.8. Samples with x=0.4, 0.5 and 0.6 quenched from 1100-1400 C to 77 K contain a single 122-type phase together with significant amounts of Fe_{1-x}Mn_xAs and FeAs2 impurity phases. These results indicate that the system is not a pseudo-binary system over the whole composition range and that the 122-type phase has a significant homogeneity range at these temperatures. Magnetic susceptibility, electrical resistivity and heat capacity measurements versus temperature of the single-phase quenched polycrystalline samples with x = 0.2 and 0.8 and for lightly doped BaMn2As2 crystals are reported.