Reactive Oxygen Species Sequestration Induced Synthesis of beta-PbO and Its Polymorphic Transformation to alpha-PbO at Atomically Thin Regimes

The emergence of attractive properties in materials at atomically thin regimes has seen an ongoing interest in twodimensional (2D) materials. An aspect that has lacked focused attention is the effect of 2D material thickness on its crystal structure. As several layered materials naturally exist in mixed metastable phases, it raises an important question of whether a specific polymorph of these mixed-phase materials will be favored at atomically thin limits. This work attempts to address this issue by employing lead monoxide as a model 2D polymorphic system. We propose a reactive oxygen species (ROS) sequestration-mediated liquid-phase exfoliation (LPE) strategy for the facile synthesis of ultrathin PbO. This is followed by a suite of microscopic and spectroscopic analyses of the PbO nanosheets that reveals the polymorphic transformation of orthorhombic (beta) PbO to its tetragonal (alpha) analogue with reduction in nanosheet thickness. The transformation process reveals an interesting crystal structure of ultrathin 2D PbO where [001]-oriented domains of alpha-PbO coexist alongside [100]-oriented regions of beta-PbO. Density functional theory (DFT) calculations support our experimental data by revealing a higher thermodynamic stability of the tetragonal phase in PbO monolayers. These findings are likely to instigate interest in carefully evaluating the crystal structures of ultrathin 2D materials while promoting research in understanding the phase transformation across a range of 2D crystals.