Activation energies for crystallization of manganese-doped (K,Na)NbO₃ thin films deposited from a chemical solution

Potassium sodium niobate (KNN) thin films are potentially useful for energy harvesting devices and for lead-free piezoelectric microelectromechanical systems. This work reports the activation energies for nucleation, growth and perovskite phase transformation from a 0.5% manganese-doped KNN 2-methoxyethanol-based solution modified with acetylacetone and excess alkali precursors. The films were annealed in a rapid thermal processor (RTP) with a hold step at temperatures from 500 to 550°C. The activation energies for perovskite transformation and growth, determined by electron micrograph observation, were 687 ± 13 and 194 ± 10 kJ/mol. The activation energy for nucleation was 341 ± 20 kJ/mol. Based on these data, crystallization in KNN is found to be nucleation-limited; thus, it should be possible to reduce the crystallization temperature by utilizing a seed layer which provides nucleation sites, provided the organics are removed from the film.