Atomic Layer Grown Zinc-Tin Oxide as an Alternative Buffer Layer for Cu₂ZnSnS₄-Based Thin Film Solar Cells: Influence...

Zn_1- Sn O (ZTO) deposited by atomic layer deposition has shown promising results as a buffer layer material for kesterite Cu₂ZnSnS₄ (CZTS) thin film solar cells. Increased performance was observed when a ZTO buffer layer was used as compared to the traditional CdS buffer, and the performance was further increased after an air annealing treatment of the absorber. In this work, we study how CZTS absorber surface treatments may influence the chemical and electronic properties at the ZTO/CZTS interface and the reactions that may occur at the absorber surface prior to atomic layer deposition of the buffer layer. For this, we have used a combination of microscopy and synchrotron-based spectroscopies with variable information depths (X-ray photoelectron spectroscopy, high-energy X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy), allowing for an in-depth analysis of the CZTS near-surface regions and bulk material properties. No significant ZTO buffer thickness variation is observed for the differently treated CZTS absorbers, and no differences are observed when comparing the bulk properties of the samples. However, the formation of SnO and compositional changes observed toward the CZTS surface upon an air annealing treatment may be linked to the modified buffer layer growth. Further, the results indicate that the initial N₂ annealing step integrated in the buffer layer growth by atomic layer deposition, which removes Na-CO species from the CZTS surface, may be useful for the ZTO/CZTS device performance.