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Electronic structure calculations within screened-exchange hybrid densityfunctional theory show that Cu(In,Ga) antisites in both CuInSe2 and CuGaSe2 arelocalized hole traps, which can be attributed to the experimentally observed N2level. In contrast, GaCu antisites and their defect complexes with coppervacancies exhibit an electron trap level, which can limit the open-circuitvoltage and efficiency in Ga-rich Cu(In,Ga)Se2 alloys. Low-temperaturephotoluminescence measurements in CuGaSe2 thin-film solar cells show afree-to-bound transition at an energy of 1.48 eV, in very good agreement withthe calculated transition energy for the GaCu antisite. Since the intrinsic DXcenter does not exhibit a pinning level within the band gap of CuInSe2,metastable DX behaviour can only be expected for GaCu antisites.

Antisite traps and metastable defects in Cu(In,Ga)Se2 thin-film solar cells studied by screened-exchange hybrid density functional theory