Two-dimensional van der Waals (vdW) ferroelectrics, renowned for their spontaneous breaking of inversion symmetry and finite electric polarization, are pivotal in nonlinear optics and low-power nanoelectronics. Prior studies primarily focused on materials exhibiting out-of-plane or in-plane ferroelectric polarization, whose rotational degrees of freedom are commonly overlooked. Herein, we experimentally validate the existence of a weak yet symmetry-allowed in-plane polarization in the low-symmetry vdW ferroelectric CuInP2S6 by rigorous structural analysis and vectorial property characterizations. Remarkably, the magnitude of this in-plane polarization is tunable via an interface-induced electric field, leading to a significant contrast in second harmonic generation between oppositely polarized domains. Based on this unique rotational capability of electric polarization, we demonstrate an electrically tunable second-order optical emission in a fabricated vdW ferroelectric capacitor. Our findings highlight the intricate interplay between crystal symmetry and tensorial physical properties, providing a novel pathway for manipulating nonlinear optical functionalities in vdW layered ferroelectrics.

Polarization-rotation-driven modulation of second harmonic generation in van der Waals layered ferroelectric CuInP2S6