Planar graphitic ZnS, buckling ZnS monolayers and rolled-up nanotubes as nonlinear optical materials: first-principles simulation.

Nonlinear optical (NLO) materials have an ability to generate new coherent light. At the present stage, three dimensional (3D) mid-infrared NLO materials suffer from various deficiencies such as low laser damage thresholds (LDTs) for AgGaQ 2 (Q = S, Se); the band gaps of most intensively studied two-dimensional (2D) NLO materials are not wide enough to avoid two-photon absorption (TPA); a steady NLO property regardless of diameter and chirality is absent in one-dimensional (1D) single-walled nanotubes (SWNTs). In this research, the electronic and second harmonic generation (SHG) properties of planar graphitic ZnS (g-ZnS) monolayer, buckling reconstructed ZnS (R-ZnS) monolayer which is synthesized in a recent experiment, and rolled-up SWNTs are investigated with first-principles simulations. Theoretical results suggest the SHG coefficients of planar g-ZnS, buckling R-ZnS and rolled-up SWNTs are comparable with that of AgGaS 2 crystals. The band gaps of planar g-ZnS and ZnS SWNTs are ∼3.8 eV, and that of buckling R-ZnS is as wide as ∼4.0 eV, indicating high LDTs and reduced TPA as NLO materials. The TPA edges can be further blue shifted by using incident light beams with a polarized electric field perpendicular to buckling R-ZnS. On the other hand, the TPA edges of ZnS SWNTs are nearly not affected by diameter and chirality. The SHG coefficients of ZnS SWNTs are much less influenced by chirality and diameter than those of SiC, GeC and BN SWNTs. Therefore, they are superior ultrathin NLO materials, and especially have a potential application in the mid-infrared regime where high-quality NLO crystals are emergently needed.