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Halogen compounds are capable of playing an important role in themanipulation of nanoparticle shapes and properties. In a new approach, weexamined the shape evolution of CdSe nanorods to hexagonal pyramids in ahot-injection synthesis under the influence of halogenated additives in theform of organic chlorine, bromine and iodine compounds. Supported by DFTcalculations, this shape evolution is explained as a result of X-type ligandcoordination to sloped and flat Cd-rich facets and an equilibrium shapestrongly influenced by halides. Synchrotron XPS measurements and TXRF resultsshow that the shape evolution is accompanied by a modification in the chemicalcomposition of the ligand sphere. Our experimental results suggest that themolecular structure of the halogenated compound is related to the degree of theeffect on both rod growth and further shape evolution. This presents a newdegree of freedom in nanoparticle shape control and highlights the role ofadditives in nanoparticle synthesis and their possible in situ formation ofligands.

Shape Evolution of CdSe Nanoparticles controlled by Halogen Compounds