Atomistic tight-binding simulations of quaternary-alloyed $$\hbox {Zn}_{x}\hbox {Cd}_{1-x}\hbox {S}_{y}\hbox {Se}_{1-y}$$ nanocrystals

Advancement of alloyed nanocrystals with attractive structural and optical properties for use in a wide range of physical, chemical, and biological applications represents a growing research field. Employing atomistic tight-binding theory combined with the virtual crystal approximation, the electronic structure and optical properties of quaternary-alloyed \(\hbox {Zn}_{{x}}\hbox {Cd}_{1-{x}} \hbox {S}_{{y}}\hbox {Se}_{1-{y}}\) nanocrystals with experimentally synthesized compositions (x and y) and sizes were investigated. Analysis of the results shows that the physical properties are mainly sensitive to the concentrations (x and y) and the diameter. With decreasing x and y contents, the optical bandgap is reduced because the contributions of the materials with narrower bulk bandgap (ZnSe and CdSe) is mostly promoted. The optical bandgap is reduced with increasing diameter due to the quantum confinement effect. The optical bandgap calculated based on tight-binding calculations shows discrepancy of less than 0.4 eV from experiment. Most importantly, the optical emission is continuously tunable across the entire visible spectrum. The conduction and valence bands are predominantly contributed by cation and anion atoms, respectively. The optical properties are obviously improved in Cd- and Se-rich quaternary \(\hbox {Zn}_{{x}}\hbox {Cd}_{1-{x}} \hbox {S}_{{y}}\hbox {Se}_{1-{y}}\) nanocrystals with large diameter. The atomistic electron–hole interactions can be hybrid-engineered by tuning either the contents (x and y) or diameter. The Stokes shift becomes more pronounced with decreasing alloy concentrations (x and y) and diameter, as described by the trend of the atomistic electron–hole exchange interaction. The present systematic study provides a new avenue to understand the unique size- and composition-dependent structural and optical properties of quaternary-alloyed \(\hbox {Zn}_{{x}}\hbox {Cd}_{1-{x}} \hbox {S}_{{y}}\hbox {Se}_{1-{y}}\) nanocrystals for broad use in multicolor bioimaging, biosensing, light-emitting diodes, solar cells, and other nanodevice applications.