Stabilized Synthesis of 2D Verbeekite: Monoclinic PdSe₂ Crystals with High Mobility and In-Plane Optical and...

PdSe₂ has a layered structure with an unusual, puckered Cairo pentagonal tiling. Its atomic bond configuration features planar 4-fold-coordinated Pd atoms and intralayer Se-Se bonds that enable polymorphic phases with distinct electronic and quantum properties, especially when atomically thin. PdSe₂ is conventionally orthorhombic, and direct synthesis of its metastable polymorphic phases is still a challenge. Here, we report an ambient-pressure chemical vapor deposition approach to synthesize metastable monoclinic PdSe₂. Monoclinic PdSe₂ is shown to be synthesized selectively under Se-deficient conditions that induce Se vacancies. These defects are shown by first-principles density functional theory calculations to reduce the free energy of the metastable monoclinic phase, thereby stabilizing it during synthesis. The structure and composition of the monoclinic PdSe₂ crystals are identified and characterized by scanning transmission electron microscopy imaging, convergent beam electron diffraction, and electron energy loss spectroscopy. Polarized Raman spectroscopy of the monoclinic PdSe₂ flakes reveals their strong in-plane optical anisotropy. Electrical transport measurements show that the monoclinic PdSe₂ exhibits n-type charge carrier conduction with electron mobilities up to ∼298 cm² V^-1 s^-1 and a strong in-plane electron mobility anisotropy of ∼1.9. The defect-mediated growth pathway identified in this work is promising for phase-selective direct synthesis of other 2D transition metal dichalcogenides.