Degradation of a Cu_xS/CdS solar cell in hot, moist air and recovery in hydrogen and air

A polycrystalline, thin-film CuxS/CdS solar cell was exposed to air saturated with water vapor at temperatures between 27 and 67 °C for up to 6 1/2 h. The short-circuit current decreased progressively from 11.7 to 1.02 mA/cm2. Subsequent heating in hydrogen at 150 °C for 680 h and in 170 °C air for 5 h restored the short-circuit current to 14.4 mA/cm2. Modeling of the measured quantum yield indicates that the degradation could be quantitatively explained by two effects: (1) the CuxS minority carrier electron diffusion length decreasing from 0.23 to 0.02 μm (±20%) and (2) the CuxS optical band gap increasing from 1.16 to 1.46 eV (±3%). The recovery was quantitatively modeled by the CuxS diffusion length increasing back to 0.24 μm and the CuxS band gap returning to 1.16 eV. A Burstein–Moss analysis shows the band-gap shift is due to the Fermi level penetration of the valence band as the measured hole concentration increased from 1.03(1020) cm−3 to 4.62(1021) cm−3 during degradation. A new band structure is proposed with six equivalent, indirect, valence band maxima located at 1.16 eV (±3%) below the conduction band edge followed by two direct maxima located at 1.28 and 1.8 eV (±3%) below the conduction band edge. A density-of-states effective mass ratio for holes of 2.0 (±30%) is found. The sharp decrease and recovery in diffusion length is explained by a transition between phonon-assisted and direct minority carrier recombination with changes in CuxS hole concentration.