Crystallography of surface nucleation and epitaxial growth of lithium triniobate on congruent lithium niobate

Abstract

The decomposition of congruent lithium niobate (LN) crystals proceeds by surface nucleation and growth of LiNb3O8 precipitates which exhibit an epitaxial orientation relationship. The same orientation relationship is observed on x-, y-, and z-cut LN substrates. The epitaxy arises from similarities between the two crystal structures and provides for an essentially continuous oxygen-ion framework from parent to product. On y-cut LN, the precipitates have a well-defined habit plane, and the interfacial misfit between the two structures is accommodated by a rectangular grid of misfit dislocations. The density, geometry, and imaging behavior of the misfit dislocations suggest that their Burgers vectors serve to accommodate the disregistry in the oxygen-ion framework. Based on these observations, it is concluded that the mechanism of formation of LiNb3O8 consists of preferential nucleation on the surface and subsequent growth, possibly by counterdiffusion of cations in a closed system where the oxygen-ion framework remains essentially fixed in space.