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J Am Chem Soc. 2018 Nov 14;140(45):15412-15418. doi: 10.1021/jacs.8b08937. Epub 2018 Oct 30.

Polymer-Directed Growth of Plasmonic Aluminum Nanocrystals.

Lu S1, Yu H1, Gottheim S2,3, Gao H4, DeSantis CJ2,3, Clark BD2,3, Yang J3,5, Jacobson CR2,3, Lu Z1,4, Nordlander P3,5,6,7, Halas NJ3,5,6,7, Liu K1.

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State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry , Jilin University , Changchun 130012 , P.R. China.
Department of Chemistry , Rice University , Houston , Texas 77005 , United States.
Laboratory for Nanophotonics , Rice University , Houston , Texas 77005 , United States.
Institute of Theoretical Chemistry , Jilin University , Changchun 130021 , P.R. China.
Department of Physics & Astronomy , Rice University , Houston , Texas 77005 , United States.
Department of Material Science and Nanoengineering , Rice University , Houston , Texas 77005 , United States.
Department of Electrical and Computer Engineering , Rice University , Houston , Texas 77005 , United States.


The challenge of controllable chemical synthesis of aluminum nanocrystals (Al NCs) has been met with only limited success. A major barrier is the absence of effective ligands to control the nucleation and growth of Al NCs. Here we demonstrate the size- and shape-controlled synthesis of monodisperse Al NCs using a polymer ligand, cumyl dithiobenzoate-terminated polystyrene (CDTB-PS). Density functional theory (DFT) calculations indicate that CDTB-PS shows selective absorption on Al{100} facets, inducing the formation of nanocubes and trigonal bipyramids. An excess of CDTB-PS, however, decreases the supersaturation of Al atoms, leading to the formation of {111} facet-terminated octahedral and triangular plates. The concentration of the catalyst, titanium (IV) isopropoxide, determines the size of Al NCs by controlling the number of seeds. Depending on nanoparticle size, the solutions of Al NCs possess distinct colors, a characteristic feature of plasmonic nanomaterials. This robust and controlled chemical synthesis of Al NCs lays a foundation for Al as a sustainable plasmonic material for current and future applications.


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