Enhancing the Charge Separation in Nanocrystalline Cu2ZnSnS4 Photocathodes for Photoelectrochemical Application: The Role of Surface Modifications.
Cu2ZnSnS4 (CZTS) colloidal inks were employed to prepare thin-film photocathodes that served as a model system to interrogate the effect of different surface treatments, viz. CdS, CdSe, and ZnSe buffer layers along with methylviologen (MV) adsorption, on the photoelectrochemical (PEC) performance using aqueous Eu(3+) redox electrolyte. PEC experiments revealed that ZnSe and CdSe overlayers outperform traditional CdS, and the additional surface modification with MV was found to further boost the charge extraction. By analyzing the photocurrent onset behavior and measuring the open circuit photopotentials, insights are gained into the nature of the observed improvements. While a more favorable conduction band offset rationalizes the improvement offered by CdSe, charge transfer through midgap states is invoked for ZnSe. Improvement offered by MV treatment is clearly caused by both the shifting of the flat-band potential and a charge-transfer mediation effect. Overall, this work suggests promising alternative surface treatments for CZTS photocathodes for PEC energy conversion.
Laboratory for Molecular Engineering of Optoelectronic Nanomaterials, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne (EPFL), Station 6, 1015-Lausanne, Switzerland.
Néstor
N
Guijarro
Laboratory for Molecular Engineering of Optoelectronic Nanomaterials, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne (EPFL), Station 6, 1015-Lausanne, Switzerland.
Mathieu S
MS
Prévot
Laboratory for Molecular Engineering of Optoelectronic Nanomaterials, Institute of Chemical Sciences and Engineering, École Polytechnique Fédérale de Lausanne (EPFL), Station 6, 1015-Lausanne, Switzerland.
Kevin
K
Sivula
CZTS; buffer layer; charge extraction; methylviologen; nanocrystal