Impact of Na Dynamics at the Cu₂ZnSn(S,Se)₄/CdS Interface During Post Low Temperature Treatment of Absorbers

Cu₂SnZn­(S,Se)₄ (CZTSSe) solar cells based on earth abundant and nontoxic elements currently achieve efficiencies exceeding 12%. It has been reported that, to obtain high efficiency devices, a post thermal treatment of absorbers or devices at temperatures ranging between 150 and 400 °C (post low temperature treatment, PLTT) is advisable. Recent findings point toward a beneficial passivation of grain boundaries with SnO_<i>x</i> or Cu-depleted surface and grain boundaries during the PLTT process, but no investigation regarding alkali doping is available, even though alkali dynamics, especially Na, are systematically reported to be crucial within the field. In this work, CZTSSe absorbers were subjected to the PLTT process under different temperatures, and solar cells were completed. We found surprisingly behavior in which efficiency decreased to nearly 0% at 200 °C during the PLTT process, being recovered or even improved at temperatures above 300 °C. This unusual behavior correlates well with the Na dynamics in the devices, especially with the in-depth distribution of Na in the active CZTSSe/CdS interface region, indicating the key importance of Na spatial distribution on device properties. We present an innovative model for Na dynamics supported by theoretical calculations and additional specially designed experiments to explain this behavior. After optimization of the PLTT process, a Se-rich CZTSSe solar cell with 8.3% efficiency was achieved

Complex Surface Chemistry of Kesterites: Cu/Zn Reordering after Low Temperature Postdeposition Annealing and Its Role in High Performance Devices

A detailed study explaining the beneficial effects of low temperature postdeposition annealing combined with selective surface etchings for Cu₂ZnSnSe₄ (CZTSe) based solar cells is presented. After performing a selective oxidizing surface etching to remove ZnSe secondary phases typically formed during the synthesis processes an additional 200 °C annealing step is necessary to increase device performance from below 3% power conversion efficiency up to 8.3% for the best case. This significant increase in efficiency can be explained by changes in the surface chemistry which results in strong improvement of the CdS/CZTSe heterojunction commonly used in this kind of absorber/buffer/window heterojunction solar cells. XPS measurements reveal that the 200 °C annealing promotes a Cu depletion and Zn enrichment of the etched CZTSe absorber surface relative to the CZTSe bulk. Raman measurements confirm a change in Cu/Zn ordering and an increase in defect density. Furthermore, TEM microstructural investigations indicate a change of grain boundaries composition by a reduction of their Cu content after the 200 °C annealing treatment. Additionally, insights in the CdS/CZTSe interface are gained showing a significant amount of Cu in the CdS buffer layer which further helps the formation of a Cu-depleted surface and seems to play an important role in the formation of the pn-heterojunction