Atomic‐Scale Visualization of Multiferroicity in Monolayer NiI₂

Abstract Progress in layered van der Waals materials has resulted in the discovery of ferromagnetic and ferroelectric materials down to the monolayer limit. Recently, evidence of the first purely 2D multiferroic material was reported in monolayer NiI₂. However, probing multiferroicity with scattering‐based and optical bulk techniques is challenging on 2D materials, and experiments on the atomic scale are needed to fully characterize the multiferroic order at the monolayer limit. Here, scanning tunneling microscopy (STM) supported by density functional theory (DFT) calculations is used to probe and characterize the multiferroic order in monolayer NiI₂. It is demonstrated that the type‐II multiferroic order displayed by NiI₂, arising from the combination of a magnetic spin spiral order and a strong spin‐orbit coupling, allows probing the multiferroic order in the STM experiments. Moreover, the magnetoelectric coupling of NiI₂ is directly probed by external electric field manipulation of the multiferroic domains. The findings establish a novel point of view to analyze magnetoelectric effects at the microscopic level, paving the way toward engineering new multiferroic orders in van der Waals materials and their heterostructures.