Origin of piezoelectricity in monolayer halogenated graphane piezoelectrics

Periodic patterning with adatoms or defect is one of the methods for opening the band gap of graphene. In particular, under certain configurations controlled by the order of hydrogen and halogen atoms attached on graphene, inversion symmetry of graphene can be broken to give piezoelectricity as well as pyroelectricity. Using first-principles calculations, we examine the structural stability and electronic properties of four polar conformations of halogenated graphane (C2HX)n to understand the origin of piezoelectricity in this two-dimensional system. The formation energies and piezoelectric coefficients manifest that the four conformations of (C2HF)n are energetically stable with considerable piezoelectricity. We find that the electronic contribution of the proper piezoelectricity in (C2HF)n is mainly related to the change of the electron distribution around F atoms. By substituting flourine with chlorine, we confirm that the piezoelectricity enhances at the expense of stability degradation.