Odd‐Stoichiometry and Secondary Phase Relations in Higher Manganese Silicides

Abstract

Higher manganese silicides (denoted as MnSiγ) are a prominent class of intermetallic compound for thermoelectric applications that crystallizes into a Nowotny Chimney Ladder (NCL) phase and constitutes a higher concentration of silicon with odd stoichiometry, typically represented by an irrational number. In this work, the genesis of Si odd stoichiometry and secondary phase relations in silicon‐rich and silicon‐deficient MnSix is presented to clarify the significance of labile (i.e., easily alterable) Si‐subsystem in inheriting the modulated lattice structure with characteristic anharmonicity. The transport properties show an interrelation to the presence of a secondary phase, which is driven by the odd stoichiometry, where the thermoelectric figure of merit (zT) is found to be optimal for MnSi1.74. The structural characterization of rapidly solidified melt‐spun ribbons and spark plasma sintered bulk specimens reveal a characteristic presence of MnSi and Si as secondary phases in Si‐deficient (x ≈ 1.5) and Si‐excess (x ≈ 2) compositions of nominal MnSix, respectively, that coexists with the major MnSiγ based NCL phase. This study provides the fundamental basis of phase evolution and the relevance of odd stoichiometry in silicon‐rich manganese silicides which exhibit fascinating phonon dynamics in optimal MnSi1.74 stoichiometry.