Synthesis, Crystal and Electronic Structure of Layered AMSb Compounds (A = Rb, Cs; M = Zn, Cd)

Abstract

Synthesis, crystal structure, thermal stability, and electronic band structure of four new metal antimonides AMSb (A = Rb, Cs; M = Zn, Cd) are reported. CsZnSb and RbZnSb crystallize in the hexagonal ZrBeSi structure type, in a P63/mmc space group (no. 194, Z = 2) and unit cell dimensions of a = 4.5588(2)/4.5466(4) Å and c = 11.9246(6)/11.0999(10) Å. CsCdSb and RbCdSb crystallize in the tetragonal PbFCl structure type in a P4/nmm space group (no. 129; Z = 2) and unit cell parameters of a = 4.8884(5)/4.8227(3) Å and c = 8.8897(9)/8.5492(7) Å. All four compounds are air‐ and water‐sensitive and are shown through DSC measurements to decompose between 975 K and 1060 K. Analysis of the calculated electronic band structure shows that the Zn‐containing antimonides are topologically trivial narrow bandgap semiconductors, whereas Cd‐containing compounds exhibit a band inversion along Γ‐Z direction.

First-principles predictions of low lattice thermal conductivity and high thermoelectric performance of AZnSb (A = Rb, Cs)

“…Many ABX compounds with 111 stoichiometry form either ZrBeSi or PbFCl type structures. [1][2][3] These compounds have been found or predicted to exhibit some useful properties for practical applications, such as topological electronic structure. [1][2][3] That's why topological materials have gained huge research interest to explore their potential applications in advanced electronic devices and their physical properties.…”

“…[1][2][3] These compounds have been found or predicted to exhibit some useful properties for practical applications, such as topological electronic structure. [1][2][3] That's why topological materials have gained huge research interest to explore their potential applications in advanced electronic devices and their physical properties. [4][5][6][7][8][9] Some of the antimony-based compounds exhibit topological behavior and its combination with other elements can crystallize in a wide range of structures, from zero to 3-dimensional motifs.…”

“…They reported that the melting or decomposition temperature of RbZnSb and CsZnSb is 975 and 1040 K, respectively. 2 From rst-principles based electronic structure calculations by using PBE functional, Owens-Baird et al also reported that the AZnSb compounds are topologically trivial narrow bandgap semiconductors. 2 The PBE functional underestimates the bandgap severely.…”

“…2 From rst-principles based electronic structure calculations by using PBE functional, Owens-Baird et al also reported that the AZnSb compounds are topologically trivial narrow bandgap semiconductors. 2 The PBE functional underestimates the bandgap severely. 28 To date, the accurate electronic structure and thermoelectric properties of these layered AZnSb compounds have not been reported.…”

How to Look for Compounds: Predictive Screening and in situ Studies in Na−Zn−Bi System

“…x Sb 9 , [48] and the discovery of AeMPn (M = Mn, Ag, Zn, Cd, Pn = Sb, Bi) [49,50] topological materials promotes interest in studying structure-property relationships in other A-M-Pn phases. Herein, we report on three new ternary compounds in the NaÀ ZnÀ Bi system, where no experimental or theoretically predicted ternary compounds have been previously reported.…”