Assembling colloidal particles using site-selective directional interactions into predetermined colloidal superlattices with desired properties is broadly sought after, but challenging to achieve. Herein, we exploit regioselective depletion interactions to engineer the directional bonding and assembly of non-spherical colloidal hybrid microparticles. We report that the crystallization of a binary colloidal mixture can be regulated by tuning the depletion conditions. Subsequently, we fabricate triblock biphasic colloids with controlled aspect ratios to achieve regioselective bonding. Without any surface treatment, these biphasic colloids assemble into various colloidal superstructures and superlattices featuring optimized pole-to-pole or centre-to-centre interactions. Additionally, we observe polymorphic crystallization, quantify the abundancy of each form using algorithms we developed and investigate the crystallization process in real time. We demonstrate selective control of attractive interactions between specific regions on an anisotropic colloid with no need of site-specific surface functionalization, leading to a general method for achieving colloidal structures with yet unforeseen arrangements and properties.
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The experimental data that support the findings of this study are available within the article, its Supplementary Information files and from the authors upon reasonable request. Raw data that support the findings of this study are publicly available at https://nyu.box.com/v/NM-Regioselective-Depletion.
The MATLAB scripts used for the polymorphism analysis are available at https://github.com/VRGParticles/Tunable-Assembly-of-Hybrid-Colloids-NatureMat-2020/ under the GNU GPL-3.0 licence.
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This work was supported through funding from Department of Energy under grant award no. DE-SC0007991. Partial support for the salary of X.Z. from the Donors of the American Chemical Society Petroleum Research Fund under grant number 56280-ND7 is acknowledged. We acknowledge M.D. Ward, D.G. Grier, J. Oh, Z. Gong, M. He, C. Shillingford and R. Rahman for helpful discussions. The Zeiss Merlin field emission SEM was acquired through the support of the NSF under award no. DMR-0923251.
The authors declare no competing interests.
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Supplementary Video Legends 1–5, Notes 1–3, Figs. 1–15, Tables 1–3 and references.
Large area observation of polymorphic formation of the brick-wall and herringbone patterns
Seed 1 formation and growth
Seed 2 and seed 3 formation and growth
Super seed formation and growth
Assembly process of Colloidal membranes
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Liu, M., Zheng, X., Grebe, V. et al. Tunable assembly of hybrid colloids induced by regioselective depletion. Nat. Mater. (2020). https://doi.org/10.1038/s41563-020-0744-2