Local structures around Mn luminescent centers in Mn-doped nanocrystals of ZnS

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Abstract
X-ray-absorption fine-structure measurements were carried out to probe the local environment surrounding Mn ions in Mn-doped nanocrystals of ZnS with different size distributions ranging from 30–35 Å to 50–55 Å. The interatomic distances between Mn and neighboring atoms, the coordination number, local disorder, and effective valency determined for the nanocrystals are compared with those in bulk Mn-doped ZnS. The Mn ions are found to substitute for the Zn sites in the host ZnS but with significant size-dependent local structural changes. The questions of Mn-cluster formation and the presence of Mn impurities on the surface of the nanocrystals are addressed. Near-edge x-ray-absorption fine structures indicate that the effective valency of Mn ions in the nanocrystals is close to +2 with a weak size dependence. These local structures are believed to be closely related to the novel optical properties observed in this new class of semiconductors.