In the last decades, the metal‐assisted growth approach of semiconductor nanowires (NWs) has shown its potential in controlling crystal properties, such as crystal structure, composition, and morphology. Recently, literature reports have shown successful semiconductor NW growth with multiphase seed particles under growth conditions. Exploring alternative metal seeds and the mechanisms for growing semiconductor NWs is an exciting research field aiming to improve the control over the crystal growth process. Herein, the gallium phosphide (GaP) NW growth using Cu as seed particles inside an environmental transmission electron microscope is studied. In particular, the transformations of the Cu‐rich seed particles during the nucleation and growth of GaP NWs are observed. The supply of a relatively high amount of Ga atoms by the precursor mixture led to a solid Cu‐rich seed particle core covered by a liquid phase. Different growth dynamics within the two‐phase seed particle resulted in local competition in NW growth. As a result, the GaP NW kinked into another growth direction by forming a new interface at the NW growth front. The generated results enable insights into fundamental processes occurring in the seed particle during growth, creating leverage points for controlling the NW morphology.
Metal−semiconductor nanoparticle heterostructures are exciting materials for photocatalytic applications. Phase and facet engineering are critical for designing highly efficient catalysts. Therefore, understanding processes occurring during the nanostructure synthesis is crucial to gain control over properties such as the surface and interface facets' orientations, morphology, and crystal structure. However, the characterization of nanostructures after the synthesis makes clarifying their formation mechanisms nontrivial and sometimes even impossible. In this study, we used an environmental transmission electron microscope with an integrated metal− organic chemical vapor deposition system to enlighten fundamental dynamic processes during the Ag-Cu 3 P-GaP nanoparticle synthesis using Ag-Cu 3 P seed particles. Our results reveal that the GaP phase nucleated at the Cu 3 P surface, and growth proceeded via a topotactic reaction involving counter-diffusion of Cu + and Ga 3+ cations. After the initial GaP growth steps, the Ag and Cu 3 P phases formed specific interfaces with the GaP growth front. GaP growth proceeded by a similar mechanism observed for the nucleation involving the diffusion of Cu atoms through/along the Ag phase toward other regions, followed by the redeposition of Cu 3 P at a specific Cu 3 P crystal facet, not in contact with the GaP phase. The Ag phase was essential for this process by acting as a medium enabling the efficient transport of Cu atoms away from and, simultaneously, Ga atoms toward the GaP-Cu 3 P interface. This study shows that enlightening fundamental processes is critical for progress in synthesizing phase-and facet-engineered multicomponent nanoparticles with tailored properties for specific applications, including catalysis.
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