Phosphorene 2D materials are composed of individual layers held together by van der Waals forces in lieu of covalent or ionic bonds that are found in most materials. There are five electrons on 3p orbitals of phosphorus atom, thus, giving rise to sp hybridization of phosphorus atom within phosphorene structure. Monolayered phosphorene exhibits the structure of a quadrangular pyramid because three electrons of P atom bond with three other P atoms covalently at 2.18 Å leaving one lone pair. Two of the phosphorus atoms are in the plane of the layer at 99° from one another, and the third phosphorus is between the layers at 103°, yielding an average angle of 102°.
According to density functional theory (DFT) calculations, phosphorene forms in a honeycomb lattice structure with notable nonplanarity in the shape of structural ridges. It is predicted that crystal structure of black phosphorus can be discriminated under high pressure. This is mostly due to the anisotropic compressibility of black phosphorus because of the asymmetrical crystal structures. Subsequently, the van der Waals bond can be greatly compressed in the z-direction. However, there is a great variation in compressibility across the orthogonal x-y plane.
It is reported that controlling the centrifugal speed of production may aid in regulating the thickness of a material. For example, centrifuging at 18000 rpm during synthesis produced phosphorene with an average diameter of 210 nm and a thickness of 2.8 ± 1.5 nm (2–7 layers).