The role of intrinsic point defects on radiative recombination in Cu(In,Ga)Se2 thin films was investigated by photoluminescence (PL) and photoluminescence excitation (PLE) spectroscopies. Experiments were performed on device-grade polycrystalline layers and single crystal thin films. PL transitions identified by others as indicating a shallow state with an ionization energy of ∼16 meV is proposed to be a transition into band tail states rather than a distinct shallow defect. The presence of deep levels contributing to radiative recombination does not necessarily preclude the material from producing a high efficiency device and may suggest the absence of dominant non-radiative recombination pathways. The band edge width as measured by PLE and the separation of this edge from defect states are suggested to be potentially effective indicators of the quality of a material. Luminescence that appears to be connected with the absence of Na in the growth process persists in high Ga alloy, Na containing materials, suggesting that Na may become ineffective in passivating or eliminating certain defects in high Ga material.

The linear polarisation of luminescence light allows conclusions on the symmetry of defects in semiconductors with non-cubic symmetry, like chalcopyrites, for which three shallow acceptors have been identified by photoluminescence. The polarisation dependent photoluminescence allows to determine the symmetry of the defects relative to the c-axis of the crystal. A simple geometrical model implies that chalcogen sites show a predominant direction perpendicular to the c-axis, while metal sites show a predominant direction parallel to the c-axis. Since all three shallow acceptors show polarization parallel to the c-axis, it can be concluded that they are situated on a metal site