Selenium-Based Molecular Cage Crystal β-P 4 Se 3 Br 2 : A Promising Candidate for Infrared Nonlinear Optical Applications

Nonlinear optical (NLO) crystals play a vital role in a wide range of applications including all-solid-state lasers and infrared (IR) NLO devices. However, existing commercially available IR NLO crystals, such as AgGaS 2 (AGS), AgGaSe 2 (AGSe), and ZnGeP 2 (ZGP), face limitations due to low laser-induced damage thresholds and undesirable two-photon absorption. This has spurred interest in developing new materials that perform well in the IR atmospheric window (2.5–25 μm). In this study, we focus on selenium-based molecular crystals, which offer advantages over sulfur-containing analogs, including a wider IR transmission range and enhanced second-harmonic generation (SHG) responses. Specifically, we synthesized β-P 4 Se 3 Br 2, a new IR NLO material derived from the centrosymmetric (CS) α-P 4 Se 3 Br 2 phase. The crystal features molecular cages interconnected by van der Waals (vdW) forces, exhibiting near-uniform alignment that enhances its NLO properties. Experimental and theoretical investigations reveal that β-P 4 Se 3 Br 2 exhibits a promising SHG response (1.1 × AGS), a large band gap (2.31 eV), and a broad transmission window (3–25 μm), making it a promising candidate for IR NLO applications. These findings highlight the potential of selenium-based molecular crystals for advancing the field of IR NLO materials.