Abstract
Multinary selenides, Sn4In5Sb9Se25 (1) and Sn6.13Pb1.87In5.00Sb10.12Bi2.88Se35 (2) were synthesized by solid-state sintering reactions. These compounds were initially observed resulting from the exploratory synthesis of multinary selenides in In–Sn–Sb–Se systems. Sn4In5Sb9Se25 crystallizes in a monoclinic lattice with a = 31.820(2) Å, b = 4.0241(3) Å, c = 19.703(2) Å, β = 114.246(5)°, and V = 2300.4(3) Å3; space group C2/m (No. 12); Z = 2. Sn6.13Pb1.87In5.00Sb10.12Bi2.88Se35 crystallizes in a monoclinic lattice with a = 31.6883(5) Å, b = 4.0709(1) Å, c = 26.5406(4) Å, β = 105.710(1)°, and V = 3295.8(2) Å3; C2/m (No. 12); Z = 2. The structures of both compounds are constructed with two building units of NaCl100-type [M2x−42+M43+Se2x+2]∞1 and NaCl111-type [M2y−23+Se3y−3]∞2. The structural anisotropy leads to a columnar or layered shape and strongly preferred orientation along [010] direction upon two compounds. These materials exhibit black color comprising a semiconducting property. Band gaps observed in electrical conductivity measurements are 0.66 eV and 0.62 eV for compound 1 and 2, respectively. UV–vis–NIR spectroscopy and the electronic band structure calculations at the density functional theory (DFT) level indicate the results of the semiconducting behaviors. Measurements of Seebeck coefficient indicates p-type semiconductors for both compounds.
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