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Title: 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 materials is well known. Yet, elucidating this influence experimentally is difficult because grains typically exhibit a large range of sizes, shapes and random relative orientations. 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 highlight 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 grains, 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 phase. 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 undermore » near-equilibrium conditions, the surface energy of the shell needs to be balanced by the increasing elastic energy through ligand passivation. With these principles, we can produce a range of multigrain nanocrystals containing distinct GB defects.« less

Authors:
 [1];  [2];  [2];  [3];  [4];  [5];  [6];  [7];  [8];  [9];  [2];  [2];  [2];  [4];  [10];  [2];  [11];  [2]
  1. Inst. for Basic Science (IBS), Seoul (Korea, Republic of). Center for Nanoparticle Research; Seoul National Univ. (Korea, Republic of); Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Kavli Energy NanoScience Institute, Berkeley, CA (United States)
  2. Inst. for Basic Science (IBS), Seoul (Korea, Republic of). Center for Nanoparticle Research; Seoul National Univ. (Korea, Republic of)
  3. Inst. for Basic Science (IBS), Seoul (Korea, Republic of). Center for Nanoparticle Research; Seoul National Univ. (Korea, Republic of). Research Institute of Advanced Materials (RIAM)
  4. Univ. of California, Berkeley, CA (United States)
  5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
  6. Inst. for Basic Science (IBS), Seoul (Korea, Republic of). Center for Nanoparticle Research; Seoul National Univ. (Korea, Republic of); Hanyang Univ., Seoul (Korea, Republic of)
  7. Pohang Accelerator Lab. (PAL) (Korea, Republic of); Pohang Univ. of Science and Technology (POSTECH) (Korea, Republic of)
  8. Korea Advanced Inst. Science and Technology (KAIST), Daejeon (Korea, Republic of)
  9. Stanford Univ., CA (United States)
  10. Inst. for Basic Science (IBS), Seoul (Korea, Republic of). Center for Nanoparticle Research; Korea Advanced Inst. Science and Technology (KAIST), Daejeon (Korea, Republic of)
  11. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Kavli Energy NanoScience Institute, Berkeley, CA (United States)
Publication Date:
Research Org.:
Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1619158
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Nature (London)
Additional Journal Information:
Journal Name: Nature (London); Journal Volume: 577; Journal Issue: 7790; Journal ID: ISSN 0028-0836
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Oh, Myoung Hwan, Cho, Min Gee, Chung, Dong Young, Park, Inchul, Kwon, Youngwook Paul, Ophus, Colin, Kim, Dokyoon, Kim, Min Gyu, Jeong, Beomgyun, Gu, X. Wendy, Jo, Jinwoung, Yoo, Ji Mun, Hong, Jaeyoung, McMains, Sara, Kang, Kisuk, Sung, Yung-Eun, Alivisatos, A Paul, and Hyeon, Taeghwan. Design and synthesis of multigrain nanocrystals via geometric misfit strain. United States: N. p., 2020. Web. https://doi.org/10.1038/s41586-019-1899-3.
Oh, Myoung Hwan, Cho, Min Gee, Chung, Dong Young, Park, Inchul, Kwon, Youngwook Paul, Ophus, Colin, Kim, Dokyoon, Kim, Min Gyu, Jeong, Beomgyun, Gu, X. Wendy, Jo, Jinwoung, Yoo, Ji Mun, Hong, Jaeyoung, McMains, Sara, Kang, Kisuk, Sung, Yung-Eun, Alivisatos, A Paul, & Hyeon, Taeghwan. Design and synthesis of multigrain nanocrystals via geometric misfit strain. United States. https://doi.org/10.1038/s41586-019-1899-3
Oh, Myoung Hwan, Cho, Min Gee, Chung, Dong Young, Park, Inchul, Kwon, Youngwook Paul, Ophus, Colin, Kim, Dokyoon, Kim, Min Gyu, Jeong, Beomgyun, Gu, X. Wendy, Jo, Jinwoung, Yoo, Ji Mun, Hong, Jaeyoung, McMains, Sara, Kang, Kisuk, Sung, Yung-Eun, Alivisatos, A Paul, and Hyeon, Taeghwan. Wed . "Design and synthesis of multigrain nanocrystals via geometric misfit strain". United States. https://doi.org/10.1038/s41586-019-1899-3. https://www.osti.gov/servlets/purl/1619158.
@article{osti_1619158,
title = {Design and synthesis of multigrain nanocrystals via geometric misfit strain},
author = {Oh, Myoung Hwan and Cho, Min Gee and Chung, Dong Young and Park, Inchul and Kwon, Youngwook Paul and Ophus, Colin and Kim, Dokyoon and Kim, Min Gyu and Jeong, Beomgyun and Gu, X. Wendy and Jo, Jinwoung and Yoo, Ji Mun and Hong, Jaeyoung and McMains, Sara and Kang, Kisuk and Sung, Yung-Eun and Alivisatos, A Paul and Hyeon, Taeghwan},
abstractNote = {The impact of topological defects associated with grain boundaries (GB defects) on the electrical, optical, magnetic, mechanical and chemical properties of nanocrystalline materials is well known. Yet, elucidating this influence experimentally is difficult because grains typically exhibit a large range of sizes, shapes and random relative orientations. 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 highlight 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 grains, 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 phase. 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 passivation. With these principles, we can produce a range of multigrain nanocrystals containing distinct GB defects.},
doi = {10.1038/s41586-019-1899-3},
journal = {Nature (London)},
number = 7790,
volume = 577,
place = {United States},
year = {2020},
month = {1}
}

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