Comprehensive landscape and simple rules for transition-metal Heusler semiconductors

Abstract

Heusler alloys, renowned for their multifunctionality and capacity for vast elemental customization, are primarily classified into half-Heusler (XYZ) and full-Heusler (X2YZ) structural types. Typically, the 18-electron half-Heusler and the 24-electron full-Heusler alloys are recognized as semiconductors, following the Slater-Pauling rule. Semiconductors are desired for many applications, but they represent a minor portion compared to the predominantly metallic and half-metallic members of the Heusler family. Recently, vacancy-filling off-stoichiometric Heuslers of ternary X1+bYZ (0 <= b <= 1) and quaternary XaX'bYZ (1 <= a + b <= 2) have emerged as a more versatile strategy. However, the flexibility associated with off-stoichiometry inevitably leads to complications, including issues with fractional filling ratios and complex site occupations. This work presents a comprehensive landscape of transition-metal-containing Heusler semiconductors, focusing on the off-stoichiometric Heuslers but seamlessly encompassing the integer-stoichiometric systems. The structural and electronic properties can be theoretically understood through a few simple rules. Many systems have been experimentally validated, showcasing their potential for applications such as thermoelectric converters.