A series of new metal chalcogenides Ba4CuGa5Q 12 (Q = S, S0.75Se0.25, Se) were synthesized using KBr flux at 750 C. The three compounds are isostructural and adopt the noncentrosymmetric space group P4Ì...21c. Crystal data are as follows: Ba4CuGa5S12, 1, a = 13.040(1) Å, c = 6.304(1) Å, and Z = 2; Ba4CuGa5S 9.00(1)Se2.92(1), 2, a = 13.1585(2) Å, c = 6.3520(2) Å, and Z = 2; Ba4CuGa5Se12, 3, a = 13.598(1) Å, c = 6.527(1) Å, and Z = 2. The three-dimensional framework in 1 is constructed by infinite columns ∞1[CuGa 4S10]7- that surround the discrete GaS 4 tetrahedra situated on a 4Ì... axis. The discrete GaS 4 tetrahedra on the stacking (112) planes and canted oriented edge-sharing CuS4 tetrahedra within the columns may account for the occurrence of strong second-harmonic generation (SHG) responses. Compounds 1-3 are transparent in the mid-infrared range and have the absorption edges at 2.82, 2.05, and 1.45 eV, respectively. The new nonlinear optical (NLO) materials are type-I nonphase matching at 693 nm and display strong SHG intensities that are ∼2.7, ∼2.6, and ∼1.1 times that of AgGaSe2 at 808 nm. Raman spectroscopic characterization of the compounds is reported.
All Science Journal Classification (ASJC) codes
- Chemical Engineering(all)
- Materials Chemistry