Experimental and Theoretical Study into Interface Structure and Band Alignment of the Cu(2)Zn(1–x)Cd(x)SnS(4) Heterointerface for Photovoltaic Applications

[Image: see text] To improve the constraints of kesterite Cu(2)ZnSnS(4) (CZTS) solar cell, such as undesirable band alignment at p–n interfaces, bandgap tuning, and fast carrier recombination, cadmium (Cd) is introduced into CZTS nanocrystals forming Cu(2)Zn(1–x)Cd(x)SnS(4) through cost-effective solution-based method without postannealing or sulfurization treatments. A synergetic experimental–theoretical approach was employed to characterize and assess the optoelectronic properties of Cu(2)Zn(1–x)Cd(x)SnS(4) materials. Tunable direct band gap energy ranging from 1.51 to 1.03 eV with high absorption coefficient was demonstrated for the Cu(2)Zn(1–x)Cd(x)SnS(4) nanocrystals with changing Zn/Cd ratio. Such bandgap engineering in Cu(2)Zn(1–x)Cd(x)SnS(4) helps in effective carrier separation at interface. Ultrafast spectroscopy reveals a longer lifetime and efficient separation of photoexcited charge carriers in Cu(2)CdSnS(4) (CCTS) nanocrystals compared to that of CZTS. We found that there exists a type-II staggered band alignment at the CZTS (CCTS)/CdS interface, from cyclic voltammetric (CV) measurements, corroborated by first-principles density functional theory (DFT) calculations, predicting smaller conduction band offset (CBO) at the CCTS/CdS interface as compared to the CZTS/CdS interface. These results point toward efficient separation of photoexcited carriers across the p–n junction in the ultrafast time scale and highlight a route to improve device performances.