The implications of grading on the emission line width of core–shell nanocrystals

An excitonic coupling with phonons leads to broadening of the emission line. The narrow excitonic emission line width observed in CdZnS/ZnS alloy core graded shell nanocrystals (NCs) with varying compositions is studied using temperature-dependent photoluminescence measurements. Contrary to the consensus that a narrow emission line width is observable with a reduction in size (due to the increased exciton–acoustic phonon coupling coefficient σ ), an increased value is noted with reduced size. Based on a theoretical approach to graded core–shell NCs, the relationship between the electron–hole wave function overlap and exciton lifetime is invoked to understand this anomaly. Smaller alloy core–shell NCs (CdZnS/ZnS-I) have a longer lifetime than larger NCs (CdZnS/ZnS-II), indicating reduced electron–hole wave function overlap for CdZnS/ZnS-I NCs and hence a larger 'effective size' of NCs, even though the actual size is smaller. The experimental findings demonstrate that graded core–shell NCs reveal an additional functionality, facilitating control of the emission line width of NCs via minimal interaction with the solid state environment. (paper)