Na2ZnGe2S6: A New Infrared Nonlinear Optical Material with Good Balance between Large Second-Harmonic Generation Response and High Laser Damage Threshold

The development of frequency-conversion technology in the infrared region is in urgent need of new excellent infrared nonlinear optical (IR NLO) materials. How to achieve a good balance between laser damage threshold (LDT) and NLO coefficient (dij) for new IR NLO candidates is still a challenge. The combination of the highly electropositive alkali metal (Na) and Zn with d10 electronic configuration into crystal structure affords one new IR NLO material, Na2ZnGe2S6. It exhibits excellent properties including a wide transparent region (0.38–22 μm), large band gap (3.25 eV), and especially a balance between a strong NLO coefficient (30-fold that of KDP) and a high LDT (6-fold that of AgGaS2), indicating a promising application in the IR region. Moreover, novel common-vertex-linked wavelike ∞[GeS3]n chains are interestingly discovered in Na2ZnGe2S6, which rarely exist in the reported thiogermanides containing alkali metals. In addition, calculated SHG density and dipole moment demonstrate that the large NLO response is mainly attributed to the cooperative effects of the [GeS4] and [ZnS4] units.