Intermixing at the absorber-buffer layer interface in thin-film solar cells: The electronic effects of point defects in Cu(In,Ga)(Se,S)₂ and Cu₂ZnSn(Se,S)₄ devices

We investigate point defects in the buffer layers CdS and ZnS that may arise from intermixing with Cu(In,Ga)(S,Se)₂ (CIGS) or Cu₂ZnSn(S,Se)₄ (CZTS) absorber layers in thin-film photovoltaics. Using hybrid functional calculations, we characterize the electrical and optical behavior of Cu, In, Ga, Se, Sn, Zn, Na, and K impurities in the buffer. We find that In and Ga substituted on the cation site act as shallow donors in CdS and tend to enhance the prevailing n-type conductivity at the interface facilitated by Cd incorporation in CIGS, whereas they are deep donors in ZnS and will be less effective dopants. Substitutional In and Ga can favorably form complexes with cation vacancies (A-centers) which may contribute to the “red kink” effect observed in some CIGS-based devices. For CZTS absorbers, we find that Zn and Sn defects substituting on the buffer cation site are electrically inactive in n-type buffers and will not supplement the donor doping at the interface as in CIGS/CdS or ZnS devices. Sn may also preferentially incorporate on the S site as a deep acceptor in n-type ZnS, which suggests possible concerns with absorber-related interfacial compensation in CZTS devices with ZnS-derived buffers. Cu, Na, and K impurities are found to all have the same qualitative behavior, most favorably acting as compensating acceptors when substituting on the cation site. Our results suggest one beneficial role of K and Na incorporation in CIGS or CZTS devices is the partial passivation of vacancy-related centers in CdS and ZnS buffers, rendering them less effective interfacial hole traps and recombination centers.