¦ van der Waals gap Septuple layer J § J || T 1/2 J 0,1 || J 0,2 || J 0,3 || J 0,4 ||

Crystal growth of MnBi 2 Te 4 has delivered the first experimental corroboration of the 3D antiferromagnetic topological insulator state. Our present results confirm that the synthesis of MnBi 2 Te 4 can be scaled-up and strengthen it as a promising experimental platform for studies of a crossover between magnetic ordering and non-trivial topology. High-quality single crystals of MnBi 2 Te 4 are grown by slow cooling within a narrow range between the melting points of Bi 2 Te 3 (586 °C) and MnBi 2 Te 4 (600 °C). Single crystal X-ray diffraction and electron microscopy reveal ubiquitous antisite defects in both cation sites and, possibly, Mn vacancies. Powders of MnBi 2 Te 4 can be obtained at subsolidus temperatures, and a complementary thermochemical study establishes a limited high-temperature range of phase stability. Nevertheless, quenched powders are stable at room temperature and exhibit long-range antiferromagnetic ordering below 24 K. The expected Mn(II) out-of-plane magnetic state is confirmed by the magnetization, X-ray photoemission, X-ray absorption and linear dichroism data. MnBi 2 Te 4 exhibits a metallic type of resistivity in the range 4.5-300 K. The compound is an n-type conductor that reaches a thermoelectric figure of merit up to ZT = 0.17. Angle-resolved photoemission experiments provide evidence for a surface state forming a gapped Dirac cone.

The layered van der Waals antiferromagnet MnBi2Te4 has been predicted to combine the band ordering of archetypical topological insulators like Bi2Te3 with the magnetism of Mn, making this material a viable candidate for the realization of various magnetic topological states. We have systematically investigated the surface electronic structure of MnBi2Te4(0001) single crystals by use of spin-and angle-resolved photoelectron spectroscopy (ARPES) experiments. In line with theoretical predictions, the results reveal a surface state in the bulk band gap and they provide evidence for the influence of exchange interaction and spin-orbit coupling on the surface electronic structure.The hallmark of a topological insulator is a single spinpolarized Dirac cone at the surface which is protected by time reversal-symmetry and originates from a band inversion in the bulk [1,2]. Notably, breaking time-reversal symmetry by magnetic order does not necessarily destroy the non-trivial topology but instead may drive the system into another topological phase. One example is the quantum anomalous Hall (QAH) state that has been observed in magnetically doped topological insulators [3]. The QAH state, in turn, may form the basis for yet more exotic electronic states, such as axion insulators [4,5] and chiral Majorana fermions [6]. Another example is the antiferromagnetic topological insulator state which is protected by a combination of time-reversal and lattice translational symmetries [7].Magnetic order in a topological insulator has mainly been achieved by doping with 3d impurities [3,8], which however inevitably gives rise to increased disorder. By contrast, the layered van der Waals material MnBi 2 Te 4 [9, 10] has recently been proposed to realize an intrinsic magnetic topological insulator [11][12][13][14], i.e. a compound that features magnetic order and a topologically non-trivial bulk band structure at the arXiv:1903.11826v2 [cond-mat.str-el]

and Anna Isaeva (anna.isaeva@tu-dresden.de) ¥ These authors contributed equally to this work. 2 Combinations of non-trivial band topology and long-range magnetic order hold promise for realizations of novel spintronic phenomena, such as the quantum anomalous Hall effect and the topological magnetoelectric effect. Following theoretical advances material candidates are emerging. Yet, a compound with a band-inverted electronic structure and an intrinsic net magnetization remains unrealized. MnBi2Te4 is a candidate for the first antiferromagnetic topological insulator and the progenitor of a modular (Bi2Te3)n(MnBi2Te4) series. For n = 1, we confirm a non-stoichiometric composition proximate to MnBi4Te7 and establish an antiferromagnetic state below 13 K followed by a state with net magnetization and ferromagnetic-like hysteresis below 5 K. Angleresolved photoemission experiments and density-functional calculations reveal a topological surface state on the MnBi4Te7(0001) surface, analogous to the non-magnetic parent compound Bi2Te3. Our results render MnBi4Te7 as a band-inverted material with an intrinsic net magnetization and a complex magnetic phase diagram providing a versatile platform for the realization of different topological phases.Soon after the discovery of topological insulators (TIs) a decade ago 1 , the role of magnetism and its potential to modify the electronic topology emerged as a central issue in the field of topological materials. Magnetic degrees of freedom provide a powerful means of tuning the decisive characteristic of any topological system: its symmetry. By now it is recognized that the interplay between magnetic order and electronic topology offers a rich playground for the realization of exotic topological states of matter, such as the quantum anomalous Hall state, 2,3 the axion insulator state, 4-6 and magnetic Weyl and nodal lines semimetals, 7-9 enabling in turn different routes to spintronic applications. [10][11][12] The non-trivial topology in paradigmatic TIs like Bi2Te3 is a result of band inversion driven by strong spin-orbit interaction. 13,14 Until recently, the interplay with magnetism in this class of systems has been mostly explored by extrinsic methods, such us doping a known TI

Structural engineering of topological bulk materials is systematically explored with regard to the incorporation of the buckled bismuth layer [Bi 2 ], which is a 2D topological insulator per se, into the layered BiTeI host structure. The previously known bismuth telluride iodides, BiTeI and Bi 2 TeI, offer physical properties relevant for spintronics. Herewith a new cousin, Bi 3 TeI (sp.gr. R3m, a = 440.12(2) pm, c = 3223.1(2) pm), joins the ranks and expands this structural family. Bi 3 TeI = [Bi 2 ][BiTeI] represents a stack with strictly alternating building blocks. Conditions for reproducible synthesis and crystal-growth of Bi 2 TeI and Bi 3 TeI are ascertained, thus yielding platelet-like crystals on the millimeter size scale and enabling direct measurements. The crystal structures of Bi 2 TeI and Bi 3 TeI are examined by X-ray diffraction and electron microscopy. DFT calculations predict metallic properties of Bi 3 TeI and an unconventional surface state residing on various surface terminations. This state emerges as a result of complex hybridization of atomic states due to their strong intermixing. Our study does not support the existence of new stacking variants Bi x TeI with x > 3; instead, it indicates a possible homogeneity range of Bi 3 TeI. The series BiTeI−Bi 2 TeI−Bi 3 TeI illustrates the influence of structural modifications on topological properties.