Ionization energies of amphoteric-doped Cu2ZnSnS4: Photovoltaic application

[Display omitted] •The ionization energies of doped-CZTS with amphoteric impurities have been obtained.•The ionization energies not cross the host bands because of a breathing mode.•It reduces the non-radiative recombination.•The maximum efficiency of these photovoltaic absorber materials has been estimated. The substitution of Cu, Sn or Zn in the quaternary Cu2ZnSnS4 semiconductor by impurities that introduce intermediate states in the energy bandgap could have important implications either for photovoltaic or spintronic applications. This allows more generation–recombination channels than for the host semiconductor. We explore and discuss this possibility by obtaining the ionization energies from total energy first-principles calculations. The three substitutions of Cu, Sn and Zn by impurities are analyzed. From these results we have found that several impurities have an amphoteric behavior with the donor and acceptor energies in the energy bandgap. In order to analyze the role of the ionization energies in both the radiative and non-radiative processes, the host energy bandgap and the acceptor and the donor energies have been obtained as a function of the inward and outward impurity-S displacements. We carried out the analysis for both the natural and synthetic CZTS. The results show that the ionization energies are similar, whereas the energy band gaps are different.