The hunt for the third acceptor in CuInSe2 and Cu(In,Ga)Se2 absorber layers

The model for intrinsic defects in Cu(In,Ga)Se-2 semiconductor layers is still under debate for the full range between CuInSe2 and CuGaSe2. It is commonly agreed by theory and experiment, that there are at least one shallow donor and two shallow acceptors. Spatially resolved photoluminescence on CuGaSe2 previously revealed a third acceptor. In this study we show with the same method that the photoluminescence peak at 0.94eV in CuInSe2, previously attributed to a third acceptor, is a phonon replica. However another pronounced peak at 0.9 eV is detected on polycrystalline CuInSe2 samples grown with high copper and selenium excess. Intensity and temperature dependent photoluminescence measurements reveal that this peak originates from a DA-transition from a shallow donor (<8 meV) into a shallow acceptor A3 (135 +/- 10) meV. The DA3 transition has three distinct phonon replicas with 28 meV spectral spacing and a Huang Rhys factor of 0.75. Complementary admittance measurements are dominated by one main step with an activation energy of 125 meV which corresponds well with the found A3 defect. The same defect is also observed in Cu(In,Ga)Se-2 samples with low gallium content. For [Ga]/([Ga] + [In])-ratios of up to 0.15 both methods show a concordant increase of the activation energy with increasing gallium content shifting the defect deeper into the bandgap. The indium vacancy V-in is discussed as a possible origin of the third acceptor level in CuInSe2 and V-III in Cu(In,Ga)Se-2.