Sequential cation exchange in nanocrystals: Preservation of crystal phase and formation of metastable phases

We demonstrate that it is possible to convert CdSe nanocrystals of a given size, shape (either spherical or rod shaped), and crystal structure (either hexagonal wurtzite, i.e., hexagonal close packed (hcp), or cubic sphalerite, i.e., face-centered cubic (fcc)), into ZnSe nanocrystals that preserve all these characteristics of the starting particles (i.e., size, shape, and crystal structure), via a sequence of two cation exchange reactions, namely, Cd ²⁺ →Cu⁺ →Zn²⁺. When starting from hexagonal wurtzite CdSe nanocrystals, the exchange of Cd²⁺ with Cu⁺ yields Cu₂Se nanocrystals in a metastable hexagonal phase, of which we could follow the transformation to the more stable fcc phase for a single nanorod, under the electron microscope. Remarkably, these metastable hcp Cu₂Se nanocrystals can be converted in solution into ZnSe nanocrystals, which yields ZnSe nanocrystals in a pure hcp phase.