Valence fluctuation of interacting electrons plays a crucial role in emergent quantum phenomena in correlated electron systems. The theoretical rationale is that this effect can drive a band insulator into a superconductor through charge redistribution around the Fermi level. However, the root cause of such a fluctuating leap in the ionic valency remains elusive. Here, we demonstrate a valence-skipping-driven insulator-to-superconductor transition and realize quasi-two-dimensional superconductivity in a van der Waals insulator GeP under pressure. This is shown to result from valence skipping of the Ge cation, altering its average valency from 3+ to 4+, turning GeP from a layered compound to a three-dimensional covalent system with superconducting critical temperature reaching its maximum of 10 K. Such a valence-skipping-induced superconductivity with a quasi-two-dimensional nature in thin samples, showing a Berezinskii-Kosterlitz-Thouless-like character, is further confirmed by angle-dependent upper-critical-field measurements. These findings provide a model system to examine competing order parameters in valence-skipping systems.
© 2022. The Author(s).