Defect physics of the quasi-two-dimensional photovoltaic semiconductor GeSe

GeSe has recently emerged as a photovoltaic absorber material due to its attractive optical and electrical properties as well as earth abundancy and low toxicity.However,the efficiency of GeSe thin-film solar cells(TFSCs)is still low compared to the Shockley–Queisser limit.Point defects are believed to play important roles in the electrical and optical properties of GeSe thin films.Here,we perform first-principles calculations to study the defect characteristics of GeSe.Our results demonstrate that no matter under the Ge-rich or Se-rich condition,the Fermi level is always located near the valence band edge,leading to the p-type conductivity of undoped samples.Under Se-rich condition,the Ge vacancy(V_(Ge))has the lowest formation energy,with a(0/2–)charge-state transition level at 0.22 eV above the valence band edge.The high density(above 10^(17)cm^(-3))and shallow level of VGeimply that it is the p-type origin of GeSe.Under Se-rich growth condition,Seihas a low formation energy in the neutral state,but it does not introduce any defect level in the band gap,suggesting that it neither contributes to electrical conductivity nor induces non-radiative recombination.In addition,Gei introduces a deep charge-state transition level,making it a possible recombination center.Therefore,we propose that the Se-rich condition should be adopted to fabricate high-efficiency GeSe solar cells.