Direct observation and control of non-classical crystallization pathways in binary colloidal systems

Abstract Crystallization stands as a prime example of self-assembly. Elementary building blocks converge, seemingly adhering to an intricate blueprint, orchestrating order from chaos. While classical theories describe crystallization as a monomer-by-monomer addition, non-classical pathways introduce...

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Main Authors: Shihao Zang, Sanjib Paul, Cheuk W. Leung, Michael S. Chen, Theodore Hueckel, Glen M. Hocky, Stefano Sacanna
Format: Article
Language:English
Published: Nature Portfolio 2025-04-01
Series:Nature Communications
Online Access:https://doi.org/10.1038/s41467-025-58959-0
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author Shihao Zang
Sanjib Paul
Cheuk W. Leung
Michael S. Chen
Theodore Hueckel
Glen M. Hocky
Stefano Sacanna
author_facet Shihao Zang
Sanjib Paul
Cheuk W. Leung
Michael S. Chen
Theodore Hueckel
Glen M. Hocky
Stefano Sacanna
author_sort Shihao Zang
collection DOAJ
description Abstract Crystallization stands as a prime example of self-assembly. Elementary building blocks converge, seemingly adhering to an intricate blueprint, orchestrating order from chaos. While classical theories describe crystallization as a monomer-by-monomer addition, non-classical pathways introduce complexity. Using microscopic charged particles as monomers, we uncover the mechanisms governing the formation of ionic colloidal crystals. Our findings reveal a two-step process, wherein metastable amorphous blobs condense from the gas phase, before evolving into small binary crystals. These small crystals then grow into large faceted structures via three simultaneous processes: addition of free monomers from bulk, capture and absorption of surrounding blobs, and oriented attachment of other crystals. These complex crystallization pathways occur both in bulk and on surfaces across a range of particle sizes and interaction strengths, resulting in a diverse array of crystal types and morphologies. Harnessing our ability to tune the interaction potential through small changes in salt concentration, we developed a continuous dialysis approach that allows fine control over the interaction strength in both time and space. This method enables us to discover and characterize various crystal structures in a single experiment, including a previously unreported low-density hollow structure and the heteroepitaxial formation of composite crystal structures.
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spelling doaj-art-9edcea0ca4af434fb99cc1ac6d9228892025-08-20T03:18:34ZengNature PortfolioNature Communications2041-17232025-04-0116111410.1038/s41467-025-58959-0Direct observation and control of non-classical crystallization pathways in binary colloidal systemsShihao Zang0Sanjib Paul1Cheuk W. Leung2Michael S. Chen3Theodore Hueckel4Glen M. Hocky5Stefano Sacanna6Department of Chemistry, New York UniversityDepartment of Chemistry, New York UniversityDepartment of Chemistry, New York UniversityDepartment of Chemistry, New York UniversityDepartment of Chemistry, New York UniversityDepartment of Chemistry, New York UniversityDepartment of Chemistry, New York UniversityAbstract Crystallization stands as a prime example of self-assembly. Elementary building blocks converge, seemingly adhering to an intricate blueprint, orchestrating order from chaos. While classical theories describe crystallization as a monomer-by-monomer addition, non-classical pathways introduce complexity. Using microscopic charged particles as monomers, we uncover the mechanisms governing the formation of ionic colloidal crystals. Our findings reveal a two-step process, wherein metastable amorphous blobs condense from the gas phase, before evolving into small binary crystals. These small crystals then grow into large faceted structures via three simultaneous processes: addition of free monomers from bulk, capture and absorption of surrounding blobs, and oriented attachment of other crystals. These complex crystallization pathways occur both in bulk and on surfaces across a range of particle sizes and interaction strengths, resulting in a diverse array of crystal types and morphologies. Harnessing our ability to tune the interaction potential through small changes in salt concentration, we developed a continuous dialysis approach that allows fine control over the interaction strength in both time and space. This method enables us to discover and characterize various crystal structures in a single experiment, including a previously unreported low-density hollow structure and the heteroepitaxial formation of composite crystal structures.https://doi.org/10.1038/s41467-025-58959-0
spellingShingle Shihao Zang
Sanjib Paul
Cheuk W. Leung
Michael S. Chen
Theodore Hueckel
Glen M. Hocky
Stefano Sacanna
Direct observation and control of non-classical crystallization pathways in binary colloidal systems
Nature Communications
title Direct observation and control of non-classical crystallization pathways in binary colloidal systems
title_full Direct observation and control of non-classical crystallization pathways in binary colloidal systems
title_fullStr Direct observation and control of non-classical crystallization pathways in binary colloidal systems
title_full_unstemmed Direct observation and control of non-classical crystallization pathways in binary colloidal systems
title_short Direct observation and control of non-classical crystallization pathways in binary colloidal systems
title_sort direct observation and control of non classical crystallization pathways in binary colloidal systems
url https://doi.org/10.1038/s41467-025-58959-0
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