Study of Nucleation and Growth in the Organometallic Synthesis of Magnetic Alloy Nanocrystals: The Role of Nucleation Rate in Size Control of CoPt3 Nanocrystals

Abstract

High quality CoPt₃ nanocrystals were synthesized via simultaneous reduction of platinum acetylacetonate and thermodecomposition of cobalt carbonyl in the presence of 1-adamantanecarboxylic acid and hexadecylamine as stabilizing agents. The high flexibility and reproducibility of the synthesis allows us to consider CoPt₃ nanocrystals as a model system for the hot organometallic synthesis of metal nanoparticles. Different experimental conditions (reaction temperature, concentration of stabilizing agents, ratio between cobalt and platinum precursors, etc.) have been investigated to reveal the processes governing the formation of the metal alloy nanocrystals. It was found that CoPt₃ nanocrystals nucleate and grow up to their final size at an early stage of the synthesis with no Ostwald ripening observed upon further heating. In this case, the nanocrystal size can be controlled only via proper balance between the rates for nucleation and for growth from the molecular precursors. Thus, the size of CoPt₃ nanocrystals can be precisely tuned from ∼3 nm up to ∼18 nm in a predictable and reproducible way. The mechanism of homogeneous nucleation, evolution of the nanocrystal ensemble in the absence of Ostwald ripening, nanocrystal faceting, and size-dependent magnetic properties are investigated and discussed on the example of CoPt₃ magnetic alloy nanocrystals. The developed approach was found to be applicable to other systems, e.g., FePt and CoPd₂ magnetic alloy nanocrystals.