ABSTRACT
A quaternary metal thioarsenate infrared (IR) nonlinear optical (NLO) compound Na4SrAs2S8 was successfully prepared by a high-temperature reaction method from stoichiometric agents. It crystallizes in the tetragonal P4n2 with the unit cell parameters a = 10.0393(3) Å, c = 6.9638(3) Å, and Z = 2, with the basic structural groups of isolated AsS4 tetrahedra. Compared with benchmark IR NLO crystal AgGaS2 (AGS), the title compound exhibits balanced optical properties of large band gap (3.05 eV vs. 2.60 eV) and considerable second harmonic generation response (0.95 × AGS). Moreover, the combined powder X-ray diffraction and differential scanning calorimetry analyses demonstrate that Na4SrAs2S8 is a congruent-melting compound with a low melting point of 668 °C, which is benefical for bulk single crystal growth. Experimental and theoretical calculation results indicate that Na4SrAs2S8 is a practically usable IR NLO crystal, also motivating the exploration of thioarsenates as high-performance IR NLO candidates.
ABSTRACT
Functional assembly of nonlinear optical (NLO) motifs with a large optical anisotropy is vital to the development of advanced NLO and birefringent materials. In this work, we highlight that, in addition to heteroatomic NLO motifs, homoatomic anionic clusters formed by aggregated anions (S, Se, Te) exhibit diverse chain-, ring-, and cage-like chemical structures as well as one-, two-, and three-dimensional motif alignments. The rich structural chemistry enables homoatomic polychalcogenides (HAPCs) to exhibit asymmetric structural features and anisotropic optical properties, with great potential for NLO and birefringent performance. Focusing on totally 55 binary HAPCs A2Qn (n = 2, 3, 4, 5; A = Na, K, Rb, Cs; Q = S, Se, Te) and their ternary analogues, we employ the state-of-the-art first-principles approach to systematically investigate the modulation evolution of their NLO and birefringent properties. Remarkably, Rb2Te3 and Na2TeSe2 exhibit rarely colossal birefringence (>1.0@10 µm) and NLO effects (>20 × AgGaS2), much larger than conventional NLO chalcogenides. Na2Te3 presents the largest birefringence to date (â¼3.48@1, 2.72@2, 2.34@10 µm), indicating the unique structural superiority of HAPC in terms of ultra-large birefringence. By mining the intrinsic mechanism, the HAPC anionic groups are identified as novel mid-infrared NLO "material genes", furnishing unique NLO and birefringent performance for the design of novel optoelectronic materials.