TY - GEN A1 - Zeugner, Alexander A1 - Kaiser, Martin A1 - Schmidt, Peer A1 - Menshchikova, Tatiana V. A1 - Rusinov, Igor P. A1 - Markelov, Anton V. A1 - Van den Broek, Wouter A1 - Chulkov, Evgueni V. A1 - Doert, Thomas A1 - Ruck, Michael A1 - Isaeva, Anna T1 - Modular Design with 2D Topological-Insulator Building Blocks: Optimized Synthesis and Crystal Growth and Crystal and Electronic Structures of BiₓTeI (x = 2, 3) T2 - Chemistry of Materials N2 - Structural engineering of topological bulk materials is systematically explored with regard to the incorporation of the buckled bismuth layer [Bi₂], which is a 2D topological insulator per se, into the layered BiTeI host structure. The previously known bismuth telluride iodides, BiTeI and Bi₂TeI, offer physical properties relevant for spintronics. Herewith a new cousin, Bi₃TeI (sp.gr. R3m, a = 440.12(2) pm, c = 3223.1(2) pm), joins the ranks and expands this structural family. Bi₃TeI = [Bi₂][BiTeI] represents a stack with strictly alternating building blocks. Conditions for reproducible synthesis and crystal-growth of Bi₂TeI and Bi₃TeI are ascertained, thus yielding platelet-like crystals on the millimeter size scale and enabling direct measurements. The crystal structures of Bi₂TeI and Bi₃TeI are examined by X-ray diffraction and electron microscopy. DFT calculations predict metallic properties of Bi₃TeI 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 BiₓTeI with x > 3; instead, it indicates a possible homogeneity range of Bi₃TeI. The series BiTeI–Bi₂TeI–Bi₃TeI illustrates the influence of structural modifications on topological properties. KW - Crytal growth KW - Topological insulator KW - Crystal structure KW - Electronic structure KW - Bismuth layered compounds Y1 - 2017 UR - http://pubs.acs.org/doi/abs/10.1021/acs.chemmater.6b05038 U6 - https://doi.org/10.1021/acs.chemmater.6b05038 SN - 0897-4756 SN - 1520-5002 VL - 29 IS - 3 SP - 1321 EP - 1337 ER -