Discovery of Real-Space Topological Ferroelectricity in Metallic Transition Metal Phosphides

Ferroelectric metals—with coexisting ferroelectricity and structural asymmetry—challenge traditional perceptions because free electrons screen electrostatic forces between ions, the driving force of breaking the spatial inversion symmetry. Despite ferroelectric metals having been unveiled one after another, topologically switchable polar objects with metallicity have never been identified so far. Here, the discovery of real-space topological ferroelectricity in metallic and non-centrosymmetric Ni₂P is reported. Protected by the rotation–inversion symmetry operation, it is found that the balanced polarity of alternately stacked polyhedra couples intimately with elemental valence states, which are verified using quantitative electron energy-loss spectroscopy. First-principles calculations reveal that an applied in-plane compressive strain creates a tunable bilinear double-well potential and reverses the polyhedral polarity on a unit-cell scale. The dual roles of nickel cations, including polar displacement inside polyhedral cages and a 3D bonding network, facilitate the coexistence of topological polarity with metallicity. In addition, the switchable in-plane polyhedral polarity gives rise to a spin–orbit-coupling-induced spin texture with large momentum-dependent spin splitting. These findings point out a new direction for exploring valence–polarity–spin correlative interactions via topological ferroelectricity in metallic systems with structural asymmetry.