摘要： To improve the constraints of kesterite Cu2ZnSnS4 (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 Cu2Zn1-xCdxSnS4 through cost-effective solution-based method without post-annealing or sulfurization treatments. A synergetic experimental-theoretical approach was employed to characterize and assess the optoelectronic properties of Cu2Zn1-xCdxSnS4 materials. Tunable direct band gap energy ranging from 1.51 eV to 1.03 eV with high absorption coefficient was demonstrated for the Cu2Zn1-xCdxSnS4 nanocrystals with changing Zn/Cd ratio. Such bandgap engineering in Cu2Zn1-xCdxSnS4 helps in effective carrier separation at interface. Ultrafast spectroscopy reveals a longer lifetime and efficient separation photo-excited charge carriers in Cu2CdSnS4 (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 towards efficient separation of photoexcited carriers across the p?n junction in the ultrafast time scale and highlight a route to improve device performances.