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Pere Miro*, Jae Hyo Han, Jinwoo Cheon, and Thomas Heine*
Hexagonal Transition-Metal Chalcogenide Nanoflakes with Pronounced Lateral Quantum Confinement
Angew. Chem. Int. Ed., 53 (46), 12624-12628
Date: Nov 10, 2014

Transition‐metal chalcogenide (TMC) nanoflakes of composition MX2 (where M=Ti, Zr and Hf; X=S and Se) crystallize preferentially in equilateral hexagons and exhibit a pronounced lateral quantum confinement. The hexagonal shape of octahedral (1T) TMC nanoflakes is the result of charge localization at the edges/vertices and the resulting Coulomb repulsion. Independent of their size, all nanoflakes have the MnX2n−2 stoichiometry and thus an unoxidized metal center which results in dopant states. These states become relevant for small nanoflakes and lead to metallic character, but for larger nanoflakes (>6 nm) the 2D monolayer properties dominate. Finally, coordination of Lewis bases at the nanoflake edges has no significant effect on the electronic structure of these species confirming the viability of colloidal synthetic approaches.

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