Stepwise Li Substitution Induced Structure Evolution and Improved Nonlinear Optical Performance for Diamond-like Sulfides

One of the key scientific issues for exploration of novel infrared nonlinear optical (NLO) crystals is to obtain ones with good hybrid NLO behaviors. Herein, we report four diamond-like Ag-based sulfides via stepwise Li substitution of Ag in Ag2ZnSnS4, including Ag2ZnSnS4 (1), (Li1.22Ag0.78)ZnSnS4 (2), (Li1.58Ag0.42)ZnSnS4 (3), and Li2ZnSnS4 (4). With the increase of Li content, the sulfide's noncentrosymmetric crystal structure changes from tetragonal I (4) over bar 2m for 1, to orthorhombic Pmn2(1) for 2 and 3, and to monoclinic Pn for 4. Accordingly, their NLO responses are improved along with the increase of Li content, viz. from non-NLO-active for 1, to non-phase-matchable for 2 and 3, and to phase-matchable for 4. Their optical band gaps also increase regularly. The relationship between their chemical compositions, crystal structures, and NLO activities is investigated by means of chemical structural analysis and theoretical calculation. This work offers a new systematic case for designing promising NLO-active compounds via rarely adopted cation's stepwise partial substitution and understanding the chemical composition-structure-NLO property relationship.