Spontaneous doping of two-dimensional NaCl films with Cr atoms: aggregation and electronic structure.

Scanning tunneling microscopy (STM) experiments combined with density functional theory (DFT) calculations reveal that deposited Cr atoms replace either Na or Cl ions, forming substituting dopants in ultrathin NaCl/Au(111) films. The Cr dopants exchange electrons with the support thus changing the electronic properties of the film and in particular the work function. The Cr atoms spontaneously aggregate near the edges of the bilayer (2L) NaCl islands, forming a new phase in the insulator with a remarkably dense population of Cr dopants. The spectra of differential conductance yield evidence that, compared to the undoped or Cr-poor 2L NaCl films on Au(111), the Cr-rich region shows different interface states, shifted image-potential states, and a reduced work function. This demonstrates the potential of doping ultrathin films to modify their adsorption properties in a desired manner.