Surface and intrinsic contributions to extinction properties of ZnSe quantum dots

This work studies extinction properties of ZnSe quantum dots terminated with either Se-surface or Zn-surface (Se-ZnSe or Zn-ZnSe QDs). In addition to commonly observed photoluminescence quenching by anionic surface sites, Se-ZnSe QDs are found to show drastic signatures of Se-surface states in their UV-visible (Vis) absorption spectra. Similar to most QDs reported in literature, monodisperse Zn-ZnSe QDs show sharp absorption features and blue-shifted yet steep absorption edge respect to the bulk bandgap. However, for monodisperse Se-ZnSe QDs, all absorption features are smeared and a low-energy tail is identified to extend to an energy window below the bulk ZnSe bandgap. Along increasing their size, a cyclic growth of ZnSe QDs switches their surface from Zn-terminated to Se-terminated ones, which confirms that the specific absorption signatures are reproducibly repeated between those of two types of the QDs. Though the extinction coefficients per unit of Se-ZnSe QDs are always larger than those of Zn-ZnSe QDs with the same size, both of them approach the same bulk limit. In addition to contribution of the lattice, extinction coefficients per nanocrystal of Zn-ZnSe QDs show an exponential term against their sizes, which is expected for quantum-confinement enhancement of electron-hole wavefunction overlapping. For Se-ZnSe QDs, there is the third term identified for their extinction coefficients per nanocrystal, which is proportional to the square of size of the QDs and consistent with surface contribution.