LiMg(IO₃)₃: an excellent SHG material designed by single-site aliovalent substitution

An excellent second harmonic generation (SHG) material, LiMg(IO₃)₃ (LMIO), has been elaborately designed from Li₂M^IV(IO₃)₆ (M^IV = Ti, Sn, and Ge) by aliovalent substitution of the central M^IV cation followed by Wyckoff position exchange. The new structure sustains the ideal-alignment of (IO₃)^- groups. Importantly, LMIO exhibits an extremely strong SHG effect of roughly 24 × KH₂PO₄ (KDP) under 1064 nm laser radiation or 1.5 × AgGaS₂ (AGS) under 2.05 μm laser radiation, which is larger than that of α-LiIO₃ (18 × KDP). The replacement of M^IV with Mg²⁺ without d-d electronic transitions induces an obviously larger band gap (4.34 eV) with a short absorption edge (285 nm). This study shows that single-site aliovalent substitution provides a new synthetic route for designing SHG materials.