On the Reaction Pathways and Growth Mechanisms of LiNbO3 Nanocrystals from the Non-Aqueous Solvothermal Alkoxide Route

Phase-pure, highly crystalline sub-50 nm LiNbO3 nanocrystals were prepared from a non-aqueous solvothermal process for 72 h at 230 degrees C and a commercial precursor solution of mixed lithium niobium ethoxide in its parent alcohol. A systematic variation of the reaction medium composition with the addition of different amounts of co-solvent including butanol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol resulted in the formation of nanocrystals of adjustable mean size and shape anisotropy, as demonstrated from XRD measurements and TEM imaging. Colloidal stability of ethanol- and water-based suspensions was evaluated from dynamic light scattering (DLS)/zeta potential studies and correlated with FTIR data. Thanks to the evolution in the nanocrystal size and shape distribution we observed, as well as to the available literature on the alkoxide chemistry, the reaction pathways and growth mechanisms were finally discussed with a special attention on the monomer formation rate, leading to the nucleation step. The polar, non-perovskite crystalline structure of LiNbO3 was also evidenced to play a major role in the nanocrystal shape anisotropy.

Automated summary

Phase-pure, highly crystalline sub-50 nm LiNbO3 nanocrystals were prepared through a non-aqueous solvothermal process, with adjustable size and shape anisotropy achieved by varying the reaction medium composition. Colloidal stability of the nanocrystals in ethanol- and water-based suspensions was assessed, and the impact of size and shape distribution on reaction pathways and growth mechanisms was discussed, highlighting the role of the polar, non-perovskite crystalline structure of LiNbO3 in nanocrystal shape anisotropy.