Correlation of Lattice Disorder with Crystallite Size and the Growth Kinetics of Mn²⁺ Doped ZnO Nanocrystals Probed by Electron Paramagnetic Resonance

The correlation of the lattice disorder with the nanocrystal average size, in ZnO nanocrystals synthesized by several different methods, has been quantitatively monitored by line shape analysis of the multifrequency electron paramagnetic resonance (EPR) spectra of low concentrations of substitutional Mn 2+ probing ions. The observed correlation between the line broadening parameter of the spectrum and the average ZnO nanocrystals size, independent of the synthesis procedure of the ZnO nanocrystals, demonstrates the dominance of the size related strain/disorder. On the basis of this result, a new method for determining the average ZnO nanocrystal size from the quantitative analysis of the EPR spectra of the Mn 2+ probes was derived. The nanocrystallization of the disordered ZnO formed by the thermal decomposition of hydrozincite was monitored using this procedure. The observed ZnO nanocrystallite growth kinetics at lower temperatures was described by a structural relaxation mechanism consisting of the local ordering by rearrangements of the atoms in the interfaces/grain boundaries, with a growth activation energy of ∼23 kJ/mol. When the nanostructured ZnO was more than 75% crystallized, another growth mechanism of the nanocrystals was found to occur, driven by the reduction of the total grain boundary energy.