Self-trapping nature of Tl nanoclusters on Si(111)-7$\times$7 surface

Abstract

We have investigated electronic and structural properties of thallium (Tl) nanoclusters formed on the Si(111)-7$\times$7 surface at room temperature (RT) by utilizing photoemission spectroscopy (PES) and high-resolution electron-energy-loss spectroscopy (HREELS) combined with first principles calculations. Our PES data show that the state S2 stemming from Si restatoms remains quite inert with Tl coverage $\theta$ while S1 from Si adatoms gradually changes, in sharp contrast with the rapidly decaying states of Na or Li nanoclusters. No Tl-induced surface state is observed until $\theta$=0.21 ML where Tl nanoclusters completely cover the faulted half unit cells (FHUCs) of the surface. These spectral behaviors of surface states and a unique loss peak L$_2$ associated with Tl in HREELS spectra indicate no strong Si-Tl bonding and are well understood in terms of gradual filling of Si dangling bonds with increasing $\theta$. Our calculational results further reveal that there are several metastable atomic structures for Tl nanoclusters at RT transforming from each other faster than 10$^{10}$ flippings per second. We thus conclude that the highly mobile Tl atoms form self-trapped nanoclusters within FHUC at RT with several metastable phases. The mobile and multi-phased nature of Tl nanoclusters not only account for all the existing experimental observations including the fuzzy scanning tunneling microscope images and a dynamical model proposed by recent x-ray study but also provides an example of self-trapping of atoms in a nanometer-scale region.