Atomic Layer Deposition on Dispersed Materials in Liquid Phase by Stoichiometrically Limited Injections

Atomic layer deposition (ALD) is a well-established vapor-phase technique for depositing thin films with high conformality and atomically precise control over thickness. Its industrial development has been largely confined to wafers and low-surface-area materials because deposition on high-surface-area materials and powders remains extremely challenging. Challenges with such materials include long deposition times, extensive purging cycles, and requirements for large excesses of precursors and expensive low-pressure equipment. Here, a simple solution-phase deposition process based on subsequent injections of stoichiometric quantities of precursor is performed using common laboratory synthesis equipment. Precisely measured precursor stoichiometries avoid any unwanted reactions in solution and ensure layer-by-layer growth with the same precision as gas-phase ALD, without any excess precursor or purging required. Identical coating qualities are achieved when comparing this technique to Al₂ O₃ deposition by fluidized-bed reactor ALD (FBR-ALD). The process is easily scaled up to coat >150 g of material using the same inexpensive laboratory glassware without any loss in coating quality. This technique is extended to sulfides and phosphates and can achieve coatings that are not possible using classic gas-phase ALD, including the deposition of phosphates with inexpensive but nonvolatile phosphoric acid.