Reversibility of (Ag,Cu)(In,Ga)Se2 electrical properties with the addition and removal of Na: Role of grain boundaries

The Na content of (Ag,Cu)(In,Ga)Se2 films was cyclically adjusted using a novel method involving cycles of water rinsing at 60 °C followed by heating in air at 200 °C to remove Na and evaporation of NaF to re-introduce Na back into the film. The low temperatures and short heating times ensure that Na is removed only from grain boundaries while leaving grain interiors unaffected. Cross-grain conductivity and Seebeck coefficient were measured during this removal procedure and both measurements decreased when Na was removed and both recovered upon the re-addition of Na, consistent with an increase in compensating donor defects in the absence of Na. These results demonstrate that Na reversibly affects the electrical properties of grain boundaries. We propose that Na reversibly passivates donor-like defects such as InCu double donors at grain boundaries.