Structural studies of phosphorus induced dimers on Si(001)

TL;DR

This study uses first-principles DFT calculations to analyze how phosphorus atoms induce structural changes and dimer formations on Si(001), providing insights relevant for quantum computing and molecular wire growth.

Contribution

It systematically investigates P-induced surface structures on Si(001) from isolated atoms to full monolayer coverage, revealing the energetically favorable configurations and their evolution.

Findings

Isolated P prefers M site placement between Si dimers.

Hetero-dimers are favored up to 1/8 monolayer coverage.

P-P ortho-dimers form at higher coverage, with surface reconstruction lifting at one monolayer.

Abstract

Renewed focus on the P-Si system due to its potential application in quantum computing and self-directed growth of molecular wires, has led us to study structural changes induced by P upon placement on Si(001)-$p(2\times 1)$. Using first-principles density functional theory (DFT) based pseudopotential method, we have performed calculations for P-Si(001) system, starting from an isolated P atom on the surface, and systematically increasing the coverage up to a full monolayer. An isolated P atom can favorably be placed on an {\bf M} site between two atoms of adjacent Si dimers belonging to the same Si dimer row. But being incorporated in the surface is even more energetically beneficial due to the participation of the {\bf M} site as a receptor for the ejected Si. Our calculations show that up to 1/8 monolayer coverage, hetero-dimer structure resulting from replacement of surface Si atoms with P is energetically favorable. Recently observed zig-zag features in STM are found to be consistent with this replacement process. As coverage increases, the hetero-dimers give way to P-P ortho-dimers on the Si dimer rows. This behavior is similar to that of Si-Si d-dimers but are to be contrasted with the Al-Al dimers, which are found between adjacent Si dimers rows and in a para-dimer arrangement. Unlike Al-Si system P-Si does not show any para to ortho transition. For both systems, the surface reconstruction is lifted at about one monolayer coverage. These calculations help us in understanding the experimental data obtained using scanning tunneling microscope.