TY - JOUR

T1 - Synthesis, Crystal and Topological Electronic Structures of New Bismuth Tellurohalides Bi2TeBr and Bi3TeBr

AU - Zeugner, Alexander

AU - Teichert, Johannes

AU - Kaiser, Martin

AU - Menshchikova, Tatiana V.

AU - Rusinov, Igor P.

AU - Markelov, Anton V.

AU - Chulkov, Evgueni V.

AU - Doert, Thomas

AU - Ruck, Michael

AU - Isaeva, Anna

PY - 2018/8/14

Y1 - 2018/8/14

N2 - Halogen substitution, that is, bromine for iodine, in the series of topological BinTeI (n = 1, 2, 3) materials was conducted in order to explore the impact of anion exchange on topological electronic structure. In this proof-of-concept study, we demonstrate the applicability of the modular view on crystal and electronic structures of new Bi2TeBr and Bi3TeBr compounds. Along with the isostructural telluroiodides, they constitute a family of layered structures that are stacked from two basic building modules, ∞ 2[Bi2] and ∞ 2[BiTeX] (X = I, Br). We present solid-state synthesis, thermochemical studies, crystal growth, and crystal-structure elucidation of Bi2TeBr [space group R3m (no. 166), a = 433.04(2) pm, c = 5081.6(3) pm] and Bi3TeBr [space group R3m (no. 160), a = 437.68(3) pm, c = 3122.9(3) pm]. First-principles calculations establish the topological nature of Bi2TeBr and Bi3TeBr. General aspects of chemical bonding appear to be similar for BinTeX (X = I, Br) with the same n, so that alternation of the global gap size upon substitution is insignificant. The complex topological inversion proceeds between the states of two distinct modules, ∞ 2[Bi2] and ∞ 2[BiTeBr]; thus, the title compounds can be seen as heterostructures built via a modular principle. Furthermore, highly disordered as well as incommensurately modulated ternary phase(s) are documented near the Bi2TeBr composition. Single-crystal X-ray diffraction experiments on BiTeBr and Bi2TeI resolve some discrepancies in prior published work.

AB - Halogen substitution, that is, bromine for iodine, in the series of topological BinTeI (n = 1, 2, 3) materials was conducted in order to explore the impact of anion exchange on topological electronic structure. In this proof-of-concept study, we demonstrate the applicability of the modular view on crystal and electronic structures of new Bi2TeBr and Bi3TeBr compounds. Along with the isostructural telluroiodides, they constitute a family of layered structures that are stacked from two basic building modules, ∞ 2[Bi2] and ∞ 2[BiTeX] (X = I, Br). We present solid-state synthesis, thermochemical studies, crystal growth, and crystal-structure elucidation of Bi2TeBr [space group R3m (no. 166), a = 433.04(2) pm, c = 5081.6(3) pm] and Bi3TeBr [space group R3m (no. 160), a = 437.68(3) pm, c = 3122.9(3) pm]. First-principles calculations establish the topological nature of Bi2TeBr and Bi3TeBr. General aspects of chemical bonding appear to be similar for BinTeX (X = I, Br) with the same n, so that alternation of the global gap size upon substitution is insignificant. The complex topological inversion proceeds between the states of two distinct modules, ∞ 2[Bi2] and ∞ 2[BiTeBr]; thus, the title compounds can be seen as heterostructures built via a modular principle. Furthermore, highly disordered as well as incommensurately modulated ternary phase(s) are documented near the Bi2TeBr composition. Single-crystal X-ray diffraction experiments on BiTeBr and Bi2TeI resolve some discrepancies in prior published work.

KW - BITEI SINGLE-CRYSTALS

KW - THERMOELECTRIC PROPERTIES

KW - CHEMISTRY

KW - PRESSURE

KW - SURFACES

KW - SCHEMES

KW - STATES

KW - BULK

KW - BII3

UR - http://www.scopus.com/inward/record.url?scp=85049840777&partnerID=8YFLogxK

UR - http://www.mendeley.com/research/synthesis-crystal-topological-electronic-structures-new-bismuth-tellurohalides-bi2tebr-bi3tebr

U2 - 10.1021/acs.chemmater.8b02005

DO - 10.1021/acs.chemmater.8b02005

M3 - Article

AN - SCOPUS:85049840777

VL - 30

SP - 5272

EP - 5284

JO - Chemistry of Materials

JF - Chemistry of Materials

SN - 0897-4756

IS - 15

ER -