Construction of $A$-$B$ hetero-layer intermetallic crystals: case studies of the 1144-phase TM-phosphides \textit{AB}(TM)$_4$P$_4$ (TM=Fe, Ru, Co, Ni

TL;DR

This paper introduces a new class of bulk intermetallic crystals with $A$-$B$ stacking, investigates their stability and properties through first-principles calculations, and experimentally synthesizes a representative compound, expanding the understanding of hetero-layer intermetallics.

Contribution

It formalizes the concept of $A$-$B$ hetero-layer stacking in bulk intermetallics, explores stable 1144-phases via first-principles calculations, and demonstrates synthesis of a high-purity example.

Findings

Identification of stable 1144-phases, especially Ru- and Fe-phosphides.

Development of a simple synthesis method for CaKRu$_4$P$_4$.

Proposal of a strategy for exploring complex multi-component compounds.

Abstract

The discovery of the 1144-phase, e.g. CaKFe$_4$As$_4$, creates opportunities to build novel intermetallics with alternative stacking of two parent compounds. Here we formalize the idea by defining a class of bulk crystalline solids with $A$-$B$ stacking (including 1144-phases and beyond), which is a generalization of hetero-structures from few-layer or thin-film semi-conductors to bulk intermetallics. Theoretically, four families of phosphides \textit{AB}(TM)$_4$P$_4$ (TM=Fe, Ru, Co, Ni) are investigated by first-principles calculations, wherein configurational, vibrational and electronic degrees of freedom are considered. It predicts a variety of stable 1144-phases (especially Ru- and Fe-phosphides). Stability rules are found and structural/electronic properties are discussed. Experimentally, we synthesize high-purity CaKRu$_4$P$_4$ as a proof of principle example. The synthetic method is simple and easily applied. Moreover, it alludes to a strategy to explore complex multi-component compounds, facilitated by a phase diagram coordinated by collective descriptors.