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Design and synthesis of multigrain nanocrystals via geometric misfit strain

Abstract

The impact of topological defects associated with grain boundaries (GB defects) on the electrical, optical, magnetic, mechanical and chemical properties of nanocrystalline materials1,2 is well known. However, elucidating this influence experimentally is difficult because grains typically exhibit a large range of sizes, shapes and random relative orientations3,4,5. Here we demonstrate that precise control of the heteroepitaxy of colloidal polyhedral nanocrystals enables ordered grain growth and can thereby produce material samples with uniform GB defects. We illustrate our approach with a multigrain nanocrystal comprising a Co3O4 nanocube core that carries a Mn3O4 shell on each facet. The individual shells are symmetry-related interconnected grains6, and the large geometric misfit between adjacent tetragonal Mn3O4 grains results in tilt boundaries at the sharp edges of the Co3O4 nanocube core that join via disclinations. We identify four design principles that govern the production of these highly ordered multigrain nanostructures. First, the shape of the substrate nanocrystal must guide the crystallographic orientation of the overgrowth phase7. Second, the size of the substrate must be smaller than the characteristic distance between the dislocations. Third, the incompatible symmetry between the overgrowth phase and the substrate increases the geometric misfit strain between the grains. Fourth, for GB formation under near-equilibrium conditions, the surface energy of the shell needs to be balanced by the increasing elastic energy through ligand passivation8,9,10. With these principles, we can produce a range of multigrain nanocrystals containing distinct GB defects.

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Fig. 1: Epitaxially guided growth and gap closing of Mn3O4 grains on a Co3O4 nanocube.
Fig. 2: Extension of SK growth to 3D polyhedral substrates.
Fig. 3: GB defects in Co3O4/Mn3O4 nanocrystals.
Fig. 4: Strain tensor measurements of Co3O4/Mn3O4 nanocrystal.

Data availability

The data that produced and support the findings of this study are available from the corresponding author upon request.

Code availability

Strain and rotation mapping using real-space peak fitting, geometric phase analysis and other Fourier filtering measurements were performed using custom MATLAB scripts. The raw image data and analysis codes are available upon reasonable request.

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Acknowledgements

Synthesis and image analysis of the nanocrystal samples were supported by the Research Center Program of IBS in Korea (IBS-R006-D1 to T.H.; IBS-R006-G1 to Y.-E.S. and K.K. The theoretical part of this work was also supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division, under contract number DE-AC02-05-CH11231 within the Physical Chemistry of Inorganic Nanostructures Program (KC3103 to A.P.A.). The computational work was supported by the Supercomputing Center/Korea Institute of Science and Technology Information with supercomputing resources including technical support (KSC-2014-C3-037 to K.K.). Work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the US Department of Energy under contract number DE-AC02-05CH11231. Experiments at PLS-II were supported in part by MSIP and POSTECH.

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M.H.O., M.G.C., A.P.A. and T.H. conceived the research. M.H.O. and M.G.C. designed and performed the experiments and analysed the results. I.P. and K.K. performed the density functional theory calculations and analysis. Y.P.K. and S.M. conducted the computer-vision-based image processing of HAADF-STEM images. C.O. conducted the strain tensor measurements for the HAADF-STEM micrographs. M.G.K. and B.J. contributed to the analysis of X-ray absorption spectroscopy and X-ray photoelectron spectroscopy data, respectively. D.Y.C., J.M.Y., D.K., X.W.G. and Y.-E.S. discussed and commented on the results. J.J. and J.H. prepared the samples for the TEM analysis. M.H.O., M.G.C., D.K., A.P.A. and T.H. wrote the manuscript. A.P.A. and T.H. supervised the project. All the authors commented on the manuscript.

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Correspondence to A. Paul Alivisatos or Taeghwan Hyeon.

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The authors declare no competing interests.

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Peer review information Nature thanks Laura Bocher, Yong Ding and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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This file contains Supplementary Methods, Supplementary Discussion, Supplementary Figures 1–17, Supplementary Table 1 and References.

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Oh, M.H., Cho, M.G., Chung, D.Y. et al. Design and synthesis of multigrain nanocrystals via geometric misfit strain. Nature 577, 359–363 (2020). https://doi.org/10.1038/s41586-019-1899-3

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