We present a comparative study that focuses on the variability of post-deposition treatments (NaF-PDT and KF-PDT) and their impact on the chemical and electronic structure of chalcopyrite thin film solar cell absorbers. For this purpose, two "extreme" chalcopyrite absorber systems are studied: Cu(In,Ga)(S,Se)2 with industrial relevance (STION), and Cu(In,Ga)Se2 with "research grade" properties (NREL). Samples were subjected to NaF-PDT and KF-PDT, and investigated using X-ray and ultraviolet photoelectron spectroscopy, Auger electron spectroscopy, and synchrotron-based soft X-ray emission spectroscopy. Considerably different alkali-induced effects are found for the two systems. In particular, we only detect a PDT-related Cu depletion on the NREL absorber surfaces (and only on those leading to high-efficiency devices). We also observe a reduction in the surface S/Se ratio for all alkali-treated STION absorbers, in addition to the presence of sulfates after the KF-PDT. After processing the PDT absorbers to fully operating cells, we find that the PDT temperature has a significant impact on the resulting device efficiencies - both the NREL and STION absorbers can result in high-efficiency and low-efficiency devices, depending on KF-PDT processing parameters. The absorbers of low-efficiency KF-PDT devices show the largest Cu surface content after PDT, causing the valence band maximum to be closer to the Fermi energy, thus possibly leading to less efficient charge-carrier separation and/or enhanced recombination at the interface. Finally, we find varying degrees of Na, K, and/or F residuals on the different absorber surfaces after PDT, indicating a potential "hidden" parameter in employing PDTs for improved solar cell performance.

The chemical structure of the Zn(O,S)/Cu(In,Ga)Se₂ interface in high-efficiency photovoltaic devices is investigated using X-ray photoelectron and Auger electron spectroscopy, as well as soft X-ray emission spectroscopy. We find that the Ga/(Ga+In) ratio at the absorber surface does not change with the formation of the Zn(O,S)/Cu(In,Ga)Se₂ interface. Furthermore, we find evidence for Zn in multiple bonding environments, including ZnS, ZnO, Zn(OH)₂, and ZnSe. We also observe dehydrogenation of the Zn(O,S) buffer layer after Ar⁺ ion treatment. Similar to high-efficiency CdS/Cu(In,Ga)Se₂ devices, intermixing occurs at the interface, with diffusion of Se into the buffer, and the formation of S-In and/or S-Ga bonds at or close to the interface.