The wurtzite to rock salt structural transformation in CdSe nanocrystals under high pressure

Structural transformations in CdSe nanocrystals are studied using high pressure x‐ray diffraction and high pressure optical absorption at room temperature. The nanocrystals undergo a wurtzite to rock salt transition analogous to that observed in bulk CdSe. Both the thermodynamics and the kinetics of the transformation, however, are significantly different in finite size. The nanocrystal phase transition pressures vary from 3.6 to 4.9 GPa for crystallites ranging from 21 to 10 Å in radius, respectively, in comparison to a value of 2.0 GPa for bulk CdSe. The size dependent data can be modeled using thermodynamics when surface energies are accounted for. Surface energies calculated in this way can be used to understand the dynamic microscopic path followed by atoms during the phase transition. X‐ray diffraction data also shows that unlike bulk CdSe, crystalline domain size is conserved upon multiple transition in the nanocrystals, indicating that the transition only nucleates once in each nanocrystal.