Electrosynthesis of Quasi-Epitaxial Crystals on Liquid Metals

Electrosynthesis of single-crystalline metallic and intermetallic particles with a preferred orientation onto liquid metal electrodes has been performed. Liquid gallium electrodes immersed in aqueous alkaline electrolytes without any molecular additive or external solid seeding substrates were used to electroreduce separately Pb²⁺, Bi³⁺, Pd²⁺, and Mn²⁺. The crystallinity, composition, and orientation of the electrodeposition products were characterized by using scanning electron microscopy, transmission electron microscopy, selected area electron diffraction, grazing incidence X-ray diffraction, and energy-dispersive X-ray spectroscopy. Electrodeposition of Pb and Bi results in the incipient formation of two-dimensional (2D) nuclei that subsequently direct the growth of Pb and Bi single crystals along the most close-packed [111] and [0001] directions, respectively. The absence of any intervening surface oxides and a low electroreduction flux are necessary to avoid polycrystalline dendrite formation. Under comparable conditions, the electrodeposition of Pd and Mn results in single-crystalline intermetallic particles at the interface. Each crystal exhibits a preferred orientation consistent with the unique atomic packing of the near-surface region of the liquid Ga. The presented study suggests a new concept in electrodeposition processes where the liquid metal structure imparts quasi-epitaxial growth in a system in which the electrode material specifically has no crystallinity or long-range order. This study is thus the first demonstration of highly oriented electrodeposition at a liquid/liquid interface under ambient conditions, highlighting the unique solvation environment of liquid metal interfaces for forming thin metallic and intermetallic films.