Co-operativity in a nanocrystalline solid-state transition

Co-operativity is a remarkable phenomenon mostly seen in biology, where initial reaction events significantly alter the propensity of subsequent reaction events, giving rise to a nonlinear tightly regulated synergistic response. Here we have found unique evidence of atomic level co-operativity in an inorganic material. A thousand-atom nanocrystal (NC) of the inorganic solid cadmium selenide exhibits strong positive co-operativity in its reaction with copper ions. A NC doped with a few copper impurities becomes highly prone to be doped even further, driving an abrupt transition of the entire NC to the copper selenide phase, as manifested by a strongly sigmoidal response in optical spectroscopy and electron diffraction measurements. The examples presented here suggest that cooperative phenomena may have an important role in the solid state, especially in the nucleation of new chemical phases, crystal growth, and other materials’ transformations.