Layered Seed-Growth of AgGe Football-like Microspheres via Precursor-Free Picosecond Laser Synthesis in Water

Hybrid particles are of great significance in terms of their adjustable optical, electronic, magnetic, thermal and mechanical properties. As a novel technique, laser ablation in liquids (LAL) is famous for its precursor-free, "clean" synthesis of hybrid particles with various materials. Till now, almost all the LAL-generated particles originate from the nucleation-growth mechanism. Seed-growth of particles similar to chemical methods seems difficult to be achieved by LAL. Here, we not only present novel patch-joint football-like AgGe microspheres with a diameter in the range of 1 ~ 7 μm achievable by laser ablation in distilled water but also find direct evidences of their layered seed growth mechanism. Many critical factors contribute to the formation of AgGe microspheres: fast laser-generated plasma process provide an excellent condition for generating large amount of Ge and Ag ions/atoms, their initial nucleation and galvanic replacement reaction, while cavitation bubble confinement plays an important role for the increase of AgGe nuclei and subsequent layered growth in water after bubble collapse. Driven by work function difference, Ge acts as nucleation agent for silver during alloy formation. This new seed-growth mechanism for LAL technique opens new opportunities to develop a large variety of novel hybrid materials with controllable properties.