Lithium Niobate Particles with a Tunable Diameter and Porosity for Optical Second Harmonic Generation

Uniform, porous particles of lithium niobate (LiNbO3) can be used as contrast agents in bioimaging, drug delivery carriers, nonlinear optical emitters, biosensors, photocatalysts and electrode materials in lithium-ion batteries. In this article, we introduce a hydrothermal method to prepare uniform, mesoporous LiNbO3 particles with a tunable diameter and porosity. These properties are each tuned by adjusting the reaction times of the hydrothermal process. This approach forms mesoporous LiNbO3 particles without the addition of organic additives (e.g., surfactants) or hard templates (e.g., silica). Formation of these LiNbO3 particles proceeds through an aqueous sol–gel reaction in which niobium hydroxide species are generated in situ and undergo a condensation reaction in the presence of lithium hydroxide to form a colloidal solution. A hydrothermal reaction using this solution resulted in the formation of uniform, solid, and semi-crystalline particles. A post-calcination step induces crystallinity in the product and transforms the particles into mesoporous materials composed of a rhombohedral LiNbO3 phase. An increase in reaction time results in an increase in the diameter of these particles from 580 to 1850 nm, but also decreases their porosity. These LiNbO3 particles were active towards second harmonic generation (SHG), and their SHG response resembled that of larger crystals of rhombohedral LiNbO3. This work also offers a viable strategy for manufacturing other materials (e.g., tantalates, titanates, niobates) with tunable dimensions and porosity that enable a broad range of applications in photonics, energy, and catalysis.