Chemical Aspects of the Candidate Antiferromagnetic Topological Insulator MnBi2Te4

High-quality single crystals of MnBi2Te4 are grown for the first time by slow cooling within a narrow range between the melting points of Bi2Te3 (586 °C) and MnBi2Te4 (600 °C). Single-crystal X-ray diffraction and electron microscopy reveal ubiquitous antisite defects in both cation sites and, possibly, Mn vacancies (Mn0.85(3)Bi2.10(3)Te4). Thermochemical studies complemented with high-temperature X-ray diffraction establish a limited high-temperature range of phase stability and metastability at room temperature. Nevertheless, the synthesis of MnBi2Te4 can be scaled-up as powders can be obtained at subsolidus temperatures and quenched at room temperature. Bulk samples exhibit long-range antiferromagnetic ordering below 24 K. The Mn(II) out-of-plane magnetic state is confirmed by the magnetization, X-ray photoemission, X-ray absorption, and linear dichroism measurements. The compound shows a metallic type of resistivity in the range 4.5–300 K and is an n-type conductor that reaches a thermoelectric figure of merit up to ZT = 0.17. Angle-resolved photoemission experiments show a surface state forming a gapped Dirac cone, thus strengthening MnBi2Te4 as a promising candidate for the intrinsic magnetic topological insulator, in accordance with theoretical predictions. The developed synthetic protocols enable further experimental studies of a crossover between magnetic ordering and nontrivial topology in bulk MnBi2Te4.