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Diffusion-Mediated Nucleation and Growth of fcc and bcc Nanocrystal Superlattices with Designable Assembly of Freestanding 3D Supercrystals

Xin Huang Orcid Logo, Elizabeth Suit Orcid Logo, Jinlong Zhu Orcid Logo, Binghui Ge, Frauke Gerdes, Christian Klinke Orcid Logo, Zhongwu Wang Orcid Logo

Journal of the American Chemical Society, Volume: 145, Issue: 8, Pages: 4500 - 4507

Swansea University Author: Christian Klinke Orcid Logo

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DOI (Published version): 10.1021/jacs.2c11120

Abstract

Diffusion-mediated assembly of octahedral PbS nanocrystals (NCs) in a confined antisolvent environment displays a primary burst nucleation and Ostwald ripening growth of rhombic bcc supercrystals, followed by a secondary seed-based nucleation and oriented attachment growth of triangle fcc supercryst...

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Published in: Journal of the American Chemical Society
ISSN: 0002-7863 1520-5126
Published: American Chemical Society (ACS) 2023
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URI: https://cronfa.swan.ac.uk/Record/cronfa62730
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spelling v2 62730 2023-02-24 Diffusion-Mediated Nucleation and Growth of fcc and bcc Nanocrystal Superlattices with Designable Assembly of Freestanding 3D Supercrystals c10c44238eabfb203111f88a965f5372 0000-0001-8558-7389 Christian Klinke Christian Klinke true false 2023-02-24 CHEM Diffusion-mediated assembly of octahedral PbS nanocrystals (NCs) in a confined antisolvent environment displays a primary burst nucleation and Ostwald ripening growth of rhombic bcc supercrystals, followed by a secondary seed-based nucleation and oriented attachment growth of triangle fcc supercrystals. As the diffusion proceeds from ethanol across a sharp interface into NC-suspended toluene, a burst nucleation of supercrystal seeds occurs, and such supercrystals are quickly developed into rhombic grains that have a bcc structure. At a critical size of 10 μm, an Ostwald ripening event appears to guide the supercrystal growth. Upon grain growth above 30 μm, the fcc supercrystals start a nucleation at two symmetrical tips of individual rhombic crystals. Such fcc supercrystals are developed with a triangle shape, and two triangles are combined with one bcc rhombus in-between to form a butterfly-like bowtie stacking structure. The fcc triangle wings grow larger at a reduction of bcc rhombus cores. As the bcc cores gradually fade, such butterfly-like bowtie crystals aggregate and undergo an oriented attachment process, leading to the formation of freestanding 3D triangle crystals that have a single fcc lattice. Analysis of experimental observations and defined diffusion parameters reveals that fast solvent diffusion and high-NC concentration promote the growth of rhombic bcc supercrystals, while slow solvent diffusion and low-NC concentration accelerate the development of triangle fcc supercrystals. Upon succeeding in designable growth of 3D fcc supercrystals, this study provides designing principles for controlled fabrication of supercrystals with desired superlattices for additional engineering and applications. Journal Article Journal of the American Chemical Society 145 8 4500 4507 American Chemical Society (ACS) 0002-7863 1520-5126 1 3 2023 2023-03-01 10.1021/jacs.2c11120 http://dx.doi.org/10.1021/jacs.2c11120 COLLEGE NANME Chemistry COLLEGE CODE CHEM Swansea University The CHEXS is supported by the NSF Awards DMR-1332208 and DMR-1829070. This work also made use of the Cornell Center for Materials Research Shared Facilities, which is supported through the NSF MRSEC program (Grant DMR-1719875). 2023-06-01T16:48:30.1827664 2023-02-24T08:56:00.3831454 Faculty of Science and Engineering School of Engineering and Applied Sciences - Chemistry Xin Huang 0000-0001-5404-4437 1 Elizabeth Suit 0000-0001-7374-9029 2 Jinlong Zhu 0000-0002-7314-8394 3 Binghui Ge 4 Frauke Gerdes 5 Christian Klinke 0000-0001-8558-7389 6 Zhongwu Wang 0000-0001-9742-5213 7
title Diffusion-Mediated Nucleation and Growth of fcc and bcc Nanocrystal Superlattices with Designable Assembly of Freestanding 3D Supercrystals
spellingShingle Diffusion-Mediated Nucleation and Growth of fcc and bcc Nanocrystal Superlattices with Designable Assembly of Freestanding 3D Supercrystals
Christian Klinke
title_short Diffusion-Mediated Nucleation and Growth of fcc and bcc Nanocrystal Superlattices with Designable Assembly of Freestanding 3D Supercrystals
title_full Diffusion-Mediated Nucleation and Growth of fcc and bcc Nanocrystal Superlattices with Designable Assembly of Freestanding 3D Supercrystals
title_fullStr Diffusion-Mediated Nucleation and Growth of fcc and bcc Nanocrystal Superlattices with Designable Assembly of Freestanding 3D Supercrystals
title_full_unstemmed Diffusion-Mediated Nucleation and Growth of fcc and bcc Nanocrystal Superlattices with Designable Assembly of Freestanding 3D Supercrystals
title_sort Diffusion-Mediated Nucleation and Growth of fcc and bcc Nanocrystal Superlattices with Designable Assembly of Freestanding 3D Supercrystals
author_id_str_mv c10c44238eabfb203111f88a965f5372
author_id_fullname_str_mv c10c44238eabfb203111f88a965f5372_***_Christian Klinke
author Christian Klinke
author2 Xin Huang
Elizabeth Suit
Jinlong Zhu
Binghui Ge
Frauke Gerdes
Christian Klinke
Zhongwu Wang
format Journal article
container_title Journal of the American Chemical Society
container_volume 145
container_issue 8
container_start_page 4500
publishDate 2023
institution Swansea University
issn 0002-7863
1520-5126
doi_str_mv 10.1021/jacs.2c11120
publisher American Chemical Society (ACS)
college_str Faculty of Science and Engineering
hierarchytype
hierarchy_top_id facultyofscienceandengineering
hierarchy_top_title Faculty of Science and Engineering
hierarchy_parent_id facultyofscienceandengineering
hierarchy_parent_title Faculty of Science and Engineering
department_str School of Engineering and Applied Sciences - Chemistry{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Chemistry
url http://dx.doi.org/10.1021/jacs.2c11120
document_store_str 0
active_str 0
description Diffusion-mediated assembly of octahedral PbS nanocrystals (NCs) in a confined antisolvent environment displays a primary burst nucleation and Ostwald ripening growth of rhombic bcc supercrystals, followed by a secondary seed-based nucleation and oriented attachment growth of triangle fcc supercrystals. As the diffusion proceeds from ethanol across a sharp interface into NC-suspended toluene, a burst nucleation of supercrystal seeds occurs, and such supercrystals are quickly developed into rhombic grains that have a bcc structure. At a critical size of 10 μm, an Ostwald ripening event appears to guide the supercrystal growth. Upon grain growth above 30 μm, the fcc supercrystals start a nucleation at two symmetrical tips of individual rhombic crystals. Such fcc supercrystals are developed with a triangle shape, and two triangles are combined with one bcc rhombus in-between to form a butterfly-like bowtie stacking structure. The fcc triangle wings grow larger at a reduction of bcc rhombus cores. As the bcc cores gradually fade, such butterfly-like bowtie crystals aggregate and undergo an oriented attachment process, leading to the formation of freestanding 3D triangle crystals that have a single fcc lattice. Analysis of experimental observations and defined diffusion parameters reveals that fast solvent diffusion and high-NC concentration promote the growth of rhombic bcc supercrystals, while slow solvent diffusion and low-NC concentration accelerate the development of triangle fcc supercrystals. Upon succeeding in designable growth of 3D fcc supercrystals, this study provides designing principles for controlled fabrication of supercrystals with desired superlattices for additional engineering and applications.
published_date 2023-03-01T16:48:28Z
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