Abstract
Structural evolution of copper oxide nanoparticles is examined, especially with respect to Ostwald ripening under electron beam irradiation. Dissolution of the smaller particles into the larger one was clearly observed at the atomic scale using advanced transmission electron microscope.
Keywords: Ostwald ripening, Atomic diffusion, Transmission Electron microscopy, Copper oxide nanoparticle, Atomic resolution image
Description
Ostwald ripening is a well-known crystal growth phenomenon, arising from unbalanced atomic diffusion from smaller nanoparticles with higher surface energy to bigger one (Voorhees 1985; Kuo et al. 2013; Ouyang et al. 2013). Transmission electron microscopy (TEM) is adequate to demonstrate the phenomenon associated with atomic diffusion and migration using state-of-the-art techniques (Bell et al. 2010). Herein, we show in-situ structural evolution in copper oxide nanoparticles (CuxO NPs), especially in terms of crystallization and Ostwald ripening under electron beam irradiation in TEM. The amorphous copper oxide, widespread residues on CVD graphene surfaces (Lupina et al. 2015), shows crystallization from non-crystalline to hexagonal-like lattice structures with random orientation during electron-beam irradiation (Fig. 1 a). When the two crystallized blue and green CuxO NPs become close to each other, Ostwald ripening occurs by atomic diffusion from the blue CuxO NP to the green one. In particular, it appears that the smaller blue CuxO NP with 2 nm in diameter rotated around 23 degree to diffuse into the larger green one just after 0.2 s acquisition time (Fig. 1b, c). On the other hand, the green CuxO NP just rotated a fraction of degree. Misorientation in the growing CuxO NP involves double reflections and blur in digital diffractograms (yellow insets of Fig. 1 c and d) and elongation on the outermost lattices (Fig. 1 d). After prolonged e-beam irradiation of approximately 10 s, it appears that the CuxO NP was transformed into the well-crystallized structure of hexagonal lattices in absence of defects like twin boundaries (Fig. 1 e).
Fig. 1.
Atomic resolution TEM images with respect to Ostwald ripening in CuxO NPs on graphene. All scale bars are 1 nm. a, b Crystallization in CuxO NPs from the amorphous phase during electron beam irradiation. The gap of acquisition time between a to b is about 6 s. b-d Ostwald ripening process between two CuxO NPs taken by 0.2 s time-series acquisition. e Crystallized CuxO NP with hexagonal lattice structures 10 s after taking d
This image provides direct evidence of Ostwald ripening regarding the phenomenon that the smaller particles have higher solubility owing to higher surface energy by showing atomic dissolution and rotation of CuxO NPs under atomic scale investigation.
Acknowledgements
Not applicable.
Authors’ contributions
NYK performed the experiment and wrote the manuscript. The author read and approved the final manuscript.
Funding
This work was supported by the Institute for Basic Science (IBS-R019-D1).
Availability of data and materials
Not applicable. “Please contact author for data requests.”
Competing interests
The authors declare that they have no competing interests.
Footnotes
Publisher’s Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
References
- Bell DC, Russo CJ, Benner G. sub-angstrom low-voltage performance of a monochromated, aberration-corrected transmission electron microscope. Microsc. Microanal. 2010;16:386. doi: 10.1017/S1431927610093670. [DOI] [PMC free article] [PubMed] [Google Scholar]
- Kuo CL, Hwang KC. Does morphology of a metal nanoparticle play a role in Ostwald ripening processes? Chem. Mater. 2013;25:365. doi: 10.1021/cm3031279. [DOI] [Google Scholar]
- Lupina Grzegorz, Kitzmann Julia, Costina Ioan, Lukosius Mindaugas, Wenger Christian, Wolff Andre, Vaziri Sam, Östling Mikael, Pasternak Iwona, Krajewska Aleksandra, Strupinski Wlodek, Kataria Satender, Gahoi Amit, Lemme Max C., Ruhl Guenther, Zoth Guenther, Luxenhofer Oliver, Mehr Wolfgang. Residual Metallic Contamination of Transferred Chemical Vapor Deposited Graphene. ACS Nano. 2015;9(5):4776–4785. doi: 10.1021/acsnano.5b01261. [DOI] [PubMed] [Google Scholar]
- Ouyang Runhai, Liu Jin-Xun, Li Wei-Xue. Atomistic Theory of Ostwald Ripening and Disintegration of Supported Metal Particles under Reaction Conditions. Journal of the American Chemical Society. 2013;135(5):1760–1771. doi: 10.1021/ja3087054. [DOI] [PubMed] [Google Scholar]
- Voorhees P. W. The theory of Ostwald ripening. Journal of Statistical Physics. 1985;38(1-2):231–252. doi: 10.1007/BF01017860. [DOI] [Google Scholar]
Associated Data
This section collects any data citations, data availability statements, or supplementary materials included in this article.
Data Availability Statement
Not applicable. “Please contact author for data requests.”