Gallium gradients in Cu(In,Ga)Se2 thin-film solar cells.

The gallium gradient in Cu(In,Ga)Se₂ (CIGS) layers, which forms during the two industrially relevant deposition routes, the sequential and co-evaporation processes, plays a key role in the device performance of CIGS thin-film modules. In this contribution, we present a comprehensive study on the formation, nature, and consequences of gallium gradients in CIGS solar cells. The formation of gallium gradients is analyzed in real time during a rapid selenization process by in situ X-ray measurements. In addition, the gallium grading of a CIGS layer grown with an in-line co-evaporation process is analyzed by means of depth profiling with mass spectrometry. This gallium gradient of a real solar cell served as input data for device simulations. Depth-dependent occurrence of lateral inhomogeneities on the µm scale in CIGS deposited by the co-evaporation process was investigated by highly spatially resolved luminescence measurements on etched CIGS samples, which revealed a dependence of the optical bandgap, the quasi-Fermi level splitting, transition levels, and the vertical gallium gradient. Transmission electron microscopy analyses of CIGS cross-sections point to a difference in gallium content in the near surface region of neighboring grains. Migration barriers for a copper-vacancy-mediated indium and gallium diffusion in CuInSe₂ and CuGaSe₂ were calculated using density functional theory. The migration barrier for the In_Cu antisite in CuGaSe₂ is significantly lower compared with the Ga_Cu antisite in CuInSe₂, which is in accordance with the experimentally observed Ga gradients in CIGS layers grown by co-evaporation and selenization processes. Copyright © 2014 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]