Theoretical and experimental investigation of stability and spectra of doped Ag:ZnSe nanocrystals.

In experiment, doped Ag:ZnSe nanocrystals (NCs) had better stability than that of ZnSe nanocrystals under ambient atmospheres in the presence of air and light illumination. However, it is difficult to explain the mechanism of better stability of Ag:ZnSe nanocrystals from the experiment perspective for doped nanocrystals are more unstable than corresponding pure nanocrystals in general. Using B3LYP/LANL2DZ method, we have investigated the geometrical structures, bonding characters, and molecular orbitals (MOs) of hexagonal and tetrahedral Ag doped ZnSe structures in theory. The results showed that the good stability of Ag:ZnSe nanocrystals can be attributed to the stronger binding between Ag and Se. Moreover, we have proved that Ag doped ZnSe nanocrystals synthesized in experiment should be substituting doped but not vacuity doped. Substituting Ag doped ZnSe molecules have the same configuration as that of the ZnSe structure, but vacuity doped Ag:ZnSe have completely different configuration than ZnSe structure due to the big size of Ag atom. In addition, through contrast of MO of ZnSe and Ag doped ZnSe, we have testified that Ag easily formed bonds with Se. The high binding energy and high probability of forming bonds with Se atom make Ag doped ZnSe nanocrystals have better stability than that of ZnSe nanocrystals.