Strain-induced structural phase transition, electric polarization and unusual electric properties in photovoltaic materials CsMI3 (M = Pb, Sn)

Abstract

The structural phase transition, ferroelectric polarization, and electric properties have been investigated for photovoltaic films CsMI₃ (M = Pb, Sn) epitaxially grown along (001) direction based on the density functional theory. The calculated results indicate that the phase diagrams of two epitaxial CsPbI₃ and CsSnI₃ films are almost identical, except critical transition strains varying slightly. The epitaxial tensile strains induce two ferroelectric phases Pmc2₁, and Pmn2₁, while the compressive strains drive two paraelectric phases P2₁2₁2₁, P2₁2₁2. The larger compressive strain enhances the ferroelectric instability in these two films, eventually rendering them another ferroelectric state Pc. Whether CsPbI₃ or CsSnI₃, the total polarization of Pmn2₁ phase comes from the main contribution of B-position cations (Pb or Sn), whereas, for Pmc2₁ phase, the main contributor is the I ion. Moreover, the epitaxial strain effects on antiferrodistortive vector, polarization and band gap of CsMI₃ (M = Pb, Sn) are further discussed. Unusual electronic properties under epitaxial strains are also revealed and interpreted.