Abstract

States with spontaneously broken symmetry can form due to Coulomb interactions in electronic systems with multiple internal degrees of freedom. Materials with several degenerate regions in the Brillouin zone—called valleys—offer a rich setting for the emergence of such states, which have potential electronic and optical applications1–4. To date, identification of these broken-symmetry phases has mostly relied on macroscopic transport or optical properties. Here we demonstrate a direct approach by visualizing the wavefunctions of bismuth surface states with a scanning tunnelling microscope. Strong spin–orbit coupling on the surface of bismuth leads to six degenerate, teardrop-shaped, hole valleys5. Our spectroscopic measurements reveal that exchange interactions fully lift this degeneracy at high magnetic field, and we are able to determine the nature of the valley ordering by imaging the broken-symmetry Landau level wavefunctions. The spatial features of singly degenerate Landau level wavefunctions near isolated defects contain unique signatures of interference between spin-textured valleys, which identify the electronic ground state as a quantum Hall ferroelectric. Our observations confirm the recent prediction6 that interactions in strongly anisotropic valley systems favour the occupation of a single valley, giving rise to emergent ferroelectricity in the surface state of bismuth. A phase of strongly interacting electrons that has a spontaneous dipole moment is seen for the first time using an approach that images the electron's wavefunction through interference at an impurity.

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