Microstructural characterization of chemical bath deposited and sputtered Zn(O,S) buffer layers

The present work aims at investigating the microstructure of Zn(O,S) buffer layers relative to their deposition route, namely either chemical bath deposition (CBD) or RF co-sputtering process (PVD) under pure Ar. The core of the study consists of cross-sectional transmission electron microscopy (TEM) characterization of the differently grown Zn(O,S) thin films on co-evaporated Cu(In,Ga)Se2 (CIGSe) absorbers. It shows that the morphology of Zn(O,S) layer deposited on CIGSe using CBD process is made of a thin layer of well oriented ZnS sphalerite-(111) and/or ZnS wurtzite-(0002) planes parallel to CIGSe chalcopyrite-(112) planes at the interface with CIGSe followed by misoriented nanometer-sized ZnS crystallites in an amorphous phase. As far as (PVD)Zn(O,S) is concerned, the TEM analyses reveal two different microstructures depending on the S-content in the films: for [S] / ([O] + [S]) = 0.6, the buffer layer is made of ZnO zincite and ZnS wurtzite crystallites grown nearly coherently to each other, with (0002) planes nearly parallel with CIGSe-(112) planes, while for [S] / ([O] + [S]) = 0.3, it is made of ZnO zincite type crystals with O atoms substituted by S atoms, with (0002) planes perfectly aligned with CIGSe-(112) planes. Such microstructural differences can explain why photovoltaic performances are dependent on the Zn(O,S) buffer layer deposition route.

► Zn(O,S) layers were grown by chemical bath (CBD) or physical vapor (PVD) deposition.
► For CBD, a 3 nm ZnS layer is followed by ZnS nano-crystallites in an amorphous phase.
► For PVD with [S] / ([O] + [S]) = 0.3, the layer has a Zn(O,S) zincite structure.
► For PVD with [S] / ([O] + [S]) = 0.6, ZnS wurtzite and ZnO zincite phases are mixed.