Abstract
Reaction of BaSe, Ga2Se3, and Sb2Se3 yielded the quaternary selenide Ba23Ga8Sb2Se38 in the form of single crystals (at 1223 K) and phase-pure powder (at 1073 K). Ba23Ga8Sb2Se38 is isostructural to the sulfide analogue Ba23Ga8Sb2S38, crystallizing in the noncentrosymmetric orthorhombic space group Cmc21 with a = 9.9825(4) Å, b = 33.4658(13) Å, c = 13.3856(5) Å, and Z = 2. The structure consists of isolated GaSe4 tetrahedra and SbSe3 trigonal pyramids, separated by Ba cations. An optical band gap of 2.31(2) eV, consistent with the red-brown colour of the crystals, was deduced from the UV–vis–NIR diffuse reflectance spectrum. Nonlinear optical measurements using a fundamental laser wavelength of 2090 nm indicated that Ba23Ga8Sb2Se38 exhibits a moderate powder second harmonic generation signal and non-type-I phase-matching behaviour.
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