Temporal variations of Cu(In,Ga)Se2 photovoltaic device properties during light exposure at various temperatures and voltage biases for times up to 100 h were analyzed using the kinetic theory of large lattice relaxations. Open-circuit voltage and p-type doping increased with charge injection and decreased with temperature at low injection conditions. Lattice relaxation can account for both trends and activation energies extracted from the data were approximately 0.9 and 1.2 eV for devices with lower and higher sodium content, respectively. In these devices, increased sodium content resulted in higher initial p-type doping with greater stability. First principles calculations providing revised activation energies for the (VSe − VCu) complex suggest that this defect does not account for the metastability observed here.

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