Insights into the Synthesis Mechanisms of Ag-Cu3P-GaP Multicomponent Nanoparticles
(2023) In ACS Nano 17(8). p.7674-7684- Abstract
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... (More)
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-Cu3P-GaP nanoparticle synthesis using Ag-Cu3P seed particles. Our results reveal that the GaP phase nucleated at the Cu3P surface, and growth proceeded via a topotactic reaction involving counter-diffusion of Cu+ and Ga3+ cations. After the initial GaP growth steps, the Ag and Cu3P 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 Cu3P at a specific Cu3P 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-Cu3P 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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- author
- Seifner, Michael S. LU ; Hu, Tianyi LU ; Snellman, Markus LU ; Jacobsson, Daniel LU ; Deppert, Knut LU ; Messing, Maria E. LU and Dick, Kimberly A. LU
- organization
- publishing date
- 2023
- type
- Contribution to journal
- publication status
- published
- subject
- keywords
- heterostructures, III−V semiconductors, in situ TEM, interfaces, ion exchange, metal−semiconductor, topotaxy
- in
- ACS Nano
- volume
- 17
- issue
- 8
- pages
- 11 pages
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- pmid:37017472
- scopus:85152199780
- ISSN
- 1936-0851
- DOI
- 10.1021/acsnano.3c00140
- language
- English
- LU publication?
- yes
- id
- 47bc93ab-f1bf-46dc-9b7d-7466aeca9c83
- date added to LUP
- 2023-07-20 12:34:17
- date last changed
- 2024-04-19 23:50:02
@article{47bc93ab-f1bf-46dc-9b7d-7466aeca9c83, abstract = {{<p>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<sub>3</sub>P-GaP nanoparticle synthesis using Ag-Cu<sub>3</sub>P seed particles. Our results reveal that the GaP phase nucleated at the Cu<sub>3</sub>P surface, and growth proceeded via a topotactic reaction involving counter-diffusion of Cu<sup>+</sup> and Ga<sup>3+</sup> cations. After the initial GaP growth steps, the Ag and Cu<sub>3</sub>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<sub>3</sub>P at a specific Cu<sub>3</sub>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<sub>3</sub>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.</p>}}, author = {{Seifner, Michael S. and Hu, Tianyi and Snellman, Markus and Jacobsson, Daniel and Deppert, Knut and Messing, Maria E. and Dick, Kimberly A.}}, issn = {{1936-0851}}, keywords = {{heterostructures; III−V semiconductors; in situ TEM; interfaces; ion exchange; metal−semiconductor; topotaxy}}, language = {{eng}}, number = {{8}}, pages = {{7674--7684}}, publisher = {{The American Chemical Society (ACS)}}, series = {{ACS Nano}}, title = {{Insights into the Synthesis Mechanisms of Ag-Cu<sub>3</sub>P-GaP Multicomponent Nanoparticles}}, url = {{http://dx.doi.org/10.1021/acsnano.3c00140}}, doi = {{10.1021/acsnano.3c00140}}, volume = {{17}}, year = {{2023}}, }