Thin ferroelectric materials hold great promise for compact nonvolatile memory and nonlinear optical and optoelectronic devices. Herein, an ultrathin in-plane ferroelectric material that exhibits a giant nonlinear optical effect, group-IV monochalcogenide SnSe, is reported. Nanometer-scale ferroelectric domains with 90/270 twin boundaries or 180 domain walls are revealed in physical-vapor-deposited SnSe by lateral piezoresponse force microscopy. Atomic structure characterization reveals both parallel and antiparallel stacking of neighboring van der Waals ferroelectric layers, leading to ferroelectric or antiferroelectric ordering. Ferroelectric domains exhibit giant nonlinear optical activity due to coherent enhancement of second-harmonic fields and the as-resulted second-harmonic generationwasobserved to be 100 times more intense than monolayer WS2 . This work demonstratesin-plane ferroelectric ordering and giant nonlinear optical activity in SnSe, which paves the way for applications in on-chip nonlinear optical components and nonvolatile memory devices.
