Polymorphism in the Ruddlesden-Popper Nickelate La₃Ni₂O₇: Discovery of a Hidden Phase with Distinctive Layer Stacking

We report the discovery of a novel form of Ruddlesden-Popper (RP) nickelate that stands as the first example of long-range, coherent polymorphism in this class of inorganic solids. Rather than the well-known, uniform stacking of perovskite blocks ubiquitously found in RP phases, this newly discovered polymorph of the bilayer RP phase La₃Ni₂O₇ adopts a novel stacking sequence in which single-layer and trilayer blocks of NiO₆ octahedra alternate in a “1313” sequence. Crystals of this new polymorph are described in space group Cmmm, although we note evidence for a competing Imam variant. Transport measurements at ambient pressure reveal metallic character with evidence of a charge density wave transition with an onset at T ≈ 134 K. The discovery of such polymorphism could reverberate to the expansive range of science and applications that rely on RP materials, particularly the recently reported signatures of superconductivity in bilayer La₃Ni₂O₇ with T_c as high as 80 K above 14 GPa.