期刊名称：Proceedings of the National Academy of Sciences
印刷版ISSN：0027-8424
电子版ISSN：1091-6490
出版年度：2021
卷号：118
期号：32
DOI：10.1073/pnas.2107588118
语种：English
出版社：The National Academy of Sciences of the United States of America
摘要：Significance
Self-assembly is one of the central themes in biologically controlled synthesis, and it also plays a pivotal role in fabricating a variety of advanced engineering materials. In particular, evaporation-induced self-assembly of colloidal particles enables versatile fabrication of highly ordered two- or three-dimensional nanostructures for optical, sensing, catalytic, and other applications. While it is well known that this process results in the formation of the face-centered cubic (fcc) lattice with the close-packed {111} plane parallel to the substrate, the crystallographic texture development of colloidal crystals is less understood. In this study, we show that the preferred <110> growth in the fcc colloidal crystals synthesized through evaporation-induced assembly is achieved through a gradual crystallographic rotation facilitated by mechanical stress-induced geometrically necessary dislocations.
Unlike crystalline atomic and ionic solids, texture development due to crystallographically preferred growth in colloidal crystals is less studied. Here we investigate the underlying mechanisms of the texture evolution in an evaporation-induced colloidal assembly process through experiments, modeling, and theoretical analysis. In this widely used approach to obtain large-area colloidal crystals, the colloidal particles are driven to the meniscus via the evaporation of a solvent or matrix precursor solution where they close-pack to form a face-centered cubic colloidal assembly. Via two-dimensional large-area crystallographic mapping, we show that the initial crystal orientation is dominated by the interaction of particles with the meniscus, resulting in the expected coalignment of the close-packed direction with the local meniscus geometry. By combining with crystal structure analysis at a single-particle level, we further reveal that, at the later stage of self-assembly, however, the colloidal crystal undergoes a gradual rotation facilitated by geometrically necessary dislocations (GNDs) and achieves a large-area uniform crystallographic orientation with the close-packed direction perpendicular to the meniscus and parallel to the growth direction. Classical slip analysis, finite element-based mechanical simulation, computational colloidal assembly modeling, and continuum theory unequivocally show that these GNDs result from the tensile stress field along the meniscus direction due to the constrained shrinkage of the colloidal crystal during drying. The generation of GNDs with specific slip systems within individual grains leads to crystallographic rotation to accommodate the mechanical stress. The mechanistic understanding reported here can be utilized to control crystallographic features of colloidal assemblies, and may provide further insights into crystallographically preferred growth in synthetic, biological, and geological crystals.
