上海科技大学知识管理系统

Non-centrosymmetric (NCS) structure is an indispensable prerequisite for second-order nonlinear optical (NLO) material. Currently, the mainstream approach for designing new NCS structures still relies on chemical substitution, necessitating an urgent infusion of fresh ideas. In this work, two isomorphic sulfides AeMn6Ga6S16 (Ae = Ca, 1; Sr, 2) are afforded by modifying the skeleton of centrosymmetric (CS) Mn2Ga2S5 via introducing strong electropositive alkaline-earth cations. Concretely, the incorporation of Ca2+/Sr2+ cations allow the elementary [MnGaS9]∞ chains reconfigure into a bumpy [MnS6]-[GaS4] layers in a new engagement manner, thus enabling the conversion from CS to NCS structure. Such modifications cause not only strong SHG responses (~1.5 × benchmark AgGaS2 @1700 nm), but also significantly feasible bandgaps (2.60–2.64 eV) compared to the sulfide Mn2Ga2S5 (1.36 eV), which ultimately facilitate ultrahigh laser-induced damage thresholds (4.4–6.6 × AgGaS2 @1064 nm for compounds 1 and 2). The present study offers an ingenious approach for the transformation of CS to NCS structure.