Abstract:
The non-stochiometric deviations in CZTS often results in certain detrimental point defects that act as
trap centers causing non-radiative recombination and potential fluctuations, eventually results in large
open circuit voltage (VOC) deficit in CZTS solar cells. Cationic substitution in CZTS layer is one of the
leading approaches to capture the great potential of kesterite solar cells for future cost-effective
photovoltaic technology. Here, chromium incorporation in CZTS is studied for cationic substitution in
CZTS layer, as it renders multiple chemical states including þ1, þ2 and þ 4 of Cu, Zn and Sn cations in
CZTS. The CZTS films determine to have good crystallinity and morphology with no significant disparity
among pristine and Cr-doped CZTS films, apart from slight shift of XRD (112) peak indicating partial
cation substitution by smaller Cr atoms. However, the Zn content is found to be decreased with
increasing Cr content in CZTS layer. Substantial enhancement in the absorption of Cr-doped CZTS films
indicate intermediate band (IB) within the band gap. Photoluminescence (PL) emission spectra strongly
suggests reduced non-radiative recombination and potential fluctuations in Cr-CZTS films. X-ray
photoelectron spectroscopy investigations reveal Zn substitution by Cr in CZTS crystal geometry. Using
nanoscale Kelvin Probe Force Microscopy (KPFM) and Conducting Atomic Force Microscopy (CAFM), we
verify the surface potential variation and nanoscale electrical conductivity in pristine and Cr-CZTS films.
Additionally, Zn substitution by Cr eventually lead to suppression of ZnSn deep level defects segregated at
grain boundaries (GBs). CAFM strongly confirms the GB passivation in Cr-CZTS films. This work widens
the opportunity of exploring potential cationic substitution in CZTS for developing high efficiency CZTS
solar cells.
