Recent advances in the determination of crystal structures and studies of optical properties of gold nanoclusters in the size range from tens to hundreds of gold atoms have started to reveal the grand evolution from gold complexes to nanoclusters and further to plasmonic nanoparticles. However, a detailed comparison of their photophysical properties is still lacking. Here, we compared the excited state behaviors of gold complexes, nanolcusters, and plasmonic nanoparticles, as well as small organic molecules by choosing four typical examples including the Au10 complex, Au25 nanocluster (1 nm metal core), 13 diameter Au nanoparticles, and Rhodamine B. To compare their photophysical behaviors, we performed steady-state absorption, photoluminescence, and femtosecond transient absorption spectroscopic measurements. It was found that gold nanoclusters behave somewhat like small molecules, showing both rapid internal conversion (<1 ps) and long-lived excited state lifetime (about 100 ns). Unlike the nanocluster form in which metal–metal transitions dominate, gold complexes showed significant charge transfer between metal atoms and surface ligands. Plasmonic gold nanoparticles, on the other hand, had electrons being heated and cooled (~100 ps time scale) after photo-excitation, and the relaxation was dominated by electron–electron scattering, electron–phonon coupling, and energy dissipation. In both nanoclusters and plasmonic nanoparticles, one can observe coherent oscillations of the metal core, but with different fundamental origins. Overall, this work provides some benchmarking features for organic dye molecules, organometallic complexes, metal nanoclusters, and plasmonic nanoparticles.
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In Situ Electron Microscopy of Transformations of Copper Nanoparticles under Plasmonic Excitation
Metal nanoparticles are attracting interest for their light-absorption properties, but such materials are known to dynamically evolve under the action of chemical and physical perturbations, resulting in changes in their structure and composition. Using a transmission electron microscope equipped for optical excitation of the specimen, the structural evolution of Cu-based nanoparticles under simultaneous electron beam irradiation and plasmonic excitation was investigated with high spatiotemporal resolution. These nanoparticles initially have a Cu core–Cu2O oxide shell structure, but over the course of imaging, they undergo hollowing via the nanoscale Kirkendall effect. We captured the nucleation of a void within the core, which then rapidly grows along specific crystallographic directions until the core is hollowed out. Hollowing is triggered by electron-beam irradiation; plasmonic excitation enhances the kinetics of the transformation likely by the effect of photothermal heating.
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- Award ID(s):
- 1828671
- NSF-PAR ID:
- 10428689
- Date Published:
- Journal Name:
- Nano Letters
- ISSN:
- 1530-6984
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract Annihilation of vacancy clusters in monolayer molybdenum diselenide (MoSe2) under electron beam irradiation is reported. In situ high‐resolution transmission electron microscopy observation reveals that the annihilation is achieved by diffusion of vacancies to the free edge near the vacancy clusters. Monte Carlo simulations confirm that it is energetically favorable for the vacancies to locate at the free edge. By computing the minimum energy path for the annihilation of one vacancy cluster as a case study, it is further shown that electron beam irradiation and pre‐stress in the suspended MoSe2monolayer are necessary for the vacancies to overcome the energy barriers for diffusion. The findings suggest a new mechanism of vacancy healing in 2D materials and broaden the capability of electron beam for defect engineering of 2D materials, a promising way of tuning their properties for engineering applications.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acs.nanolett.3c01474
