Defect depth-profiling in kesterite absorber by means of chemical etching and surface analysis

A method to probe the depth morphology, defect profile and possible secondary phases in a thin fil semiconductor is presented, taking a standard Kesterite film as an example. Using a top-down approach based on a previously reported controlled Methanol-Br2 chemical etching, well-defined slabs of a state of the art Kesterite absorber are fabricated. The analysis of their morphology both by Scanning Electron Microscopy and 3D optical Profilometry reveals the extent of a previously reported poor film morphology toward the back interface, and we are able to determine that more than 50% of a standard absorber is disconnected from the substrate. More importantly, these etched films are subsequently analyzed by surface sensitive techniques such as X-ray Photoelectron Spectroscopy and UV-Raman analysis. An accurate composition profile is established, and for the first time, a direct observation of the defects’ nature and their depth profiling in Kesterite is made possible. While VCu are found with a constant amount throughout the absorber, indicating a homogenous carrier concentration, a prevalence of the ZnSn defect is observed with a steep gradient toward the back interface, associated with an increase in the SnSe2 secondary phase. With bulk defects being often pointed out as the intrinsic limitation of this material, this result highlights what possibly is the main impediment of Kesterite solar cells, and a critical point to address in the design of future devices. Beyond the case of Kesterite absorbers, the method presented here offers a combination of simplicity, tunability and versatility making a straightforward transfer to other emerging thin film absorbers feasible, and it could possibly be an important tool in their future performance assessment and comparison.