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Ordered Two-Dimensional Superstructures of Colloidal Octapod-Shaped Nanocrystals on Flat Substrates

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Soft Condensed Matter, Debye Institute for Nanomaterials Science, Utrecht University, Princetonplein 5, 3584 CC Utrecht, The Netherlands
Istituto Italiano di Tecnologia (IIT), Via Morego 30, 16163 Genova, Italy
*E-mail: (W.Q.) [email protected]; (M.D.) [email protected]
Cite this: Nano Lett. 2012, 12, 10, 5299–5303
Publication Date (Web):August 31, 2012
Copyright © 2012 American Chemical Society

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    We studied crystal structures in a monolayer consisting of anisotropic branched colloidal (nano)octapods. Experimentally, octapods were observed to form a monolayer on a substrate with a square-lattice crystal structure by drop-casting and fast evaporation of solvent. The experimental results were analyzed by Monte Carlo simulations using a hard octapod model consisting of four interpenetrating spherocylinders. We confirmed by means of free-energy calculations that crystal structures with a (binary-lattice) square morphology are indeed thermodynamically stable at high densities. The effect of the pod length-to-diameter ratio on the crystal structures was also considered and we used this to constructed the phase diagram for these hard octapods. In addition to the (binary-lattice) square crystal phase, a rhombic crystal and a hexagonal plastic-crystal (rotator) phase were obtained. Our phase diagram may prove instrumental in guiding future experimental studies.

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