Grain boundaries are not the source of Urbach tails in Cu(In,Ga)Se2 absorbers

The presence of Urbach tails in Cu(In,Ga)Se2 (CIGSe) absorbers has been identified as a limiting factor for the performance of the CIGSe solar cells. The tail states contribute to both radiative and non-radiative recombination processes, ultimately leading to a reduction in the open-circuit voltage and, consequently, decreasing the overall efficiency of CIGSe devices. Urbach tails result from structural and thermal disorders. The Urbach tails can be characterized by the Urbach energy, which is associated with the magnitude of the tail states. Within polycrystalline CIGSe absorbers, grain boundaries can be considered as structural disorder and, therefore, can potentially contribute to the Urbach tails. In fact, it has been proposed that the band bending at grain boundaries contribute significantly to the tail states. This study focuses on examining the correlation between Urbach tails and the band bending at the grain boundaries. The Urbach energies of the CIGSe samples are extracted from photoluminescence (PL) measurements, which reveal that the introduction of Sodium (Na) into the material can lead to a reduction in the Urbach energy, and an even further decrease can be achieved through the RbF post-deposition treatment. The band bending at the grain boundaries is investigated by Kelvin probe force microscopy measurements. A thorough statistical analysis of more than 340 grain boundaries does not show any correlation between Urbach tails and grain boundaries. We measure small band bending values at the grain boundaries, in the range of the thermal energy (26 meV at room temperature). Furthermore, our intensity dependent PL measurements indicate that Urbach tails are, at least in part, a result of electrostatic potential fluctuations. This supports the model that the introduction of alkali elements mainly decreases the magnitude of electrostatic potential fluctuations, resulting in a subsequent reduction in the Urbach energy.