Large Non‐Resonant Infrared Optical Second Harmonic Generation in Bulk Crystals of Van der Waals Semiconductor, SnP₂Se₆

Abstract 2D van der Waals (vdW) materials have emerged as a highly promising candidates for nonlinear optical (NLO) applications. This study presents the synthesis, comprehensive linear optical, and optical second harmonic generation (SHG) characterization of a novel 2D vdW semiconductor SnP 2 Se 6 in its bulk single crystal form. It exhibits an indirect bandgap of ≈1.47 eV and an exceptional non‐resonant SHG coefficient of d 33 ∼ −222 ± 30 pm V −1 at a fundamental wavelength of 2 µm, which is ≈7 times larger than that of the commercial AgGaSe 2 with a comparable bandgap. Density functional theory (DFT) calculations of the linear and nonlinear optical properties exhibit reasonable agreement with the experimental measurements, revealing the chemical origin of the enhanced properties. Moreover, SnP 2 Se 6 can exhibit both type‐I and type‐II phase matching over a wide spectral range, fulfilling one of the key criteria for an ideal NLO crystal. These exceptional properties position SnP 2 Se 6 as a highly promising candidate for NLO applications.