Lithium niobate particles with a tunable diameter and porosity for optical second harmonic generation

Abstract

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.