Evidence for 2-D pi-bonded Surface Reconstructions on Si(111)

TL;DR

This paper proposes a silicene-like 2-D pi-bonded surface reconstruction on Si(111) that explains experimental paradoxes and introduces a new bonding model involving significant sp2-sp3 hybridization and extended pi-bonded structures.

Contribution

It introduces a novel silicene-like polymorph of Si(111) with a unique bonding structure, resolving longstanding experimental inconsistencies.

Findings

Consistent with known surface state charge densities

Features a 'faulted' honeycomb Si atom motif

Reveals a 2-D pi-bonded structure with non-covalent interactions

Abstract

A silicene-like polymorph of the Si111 7x7 surface is proposed that resolves numerous experimental paradoxes and inconsistencies arising over the past 34 years. An analysis of the three established surface state charge densities from atom resolved spectroscopic imaging, including the 'forgotten' surface state at ~ -0.4 eV, shows features that are consistent with well studied 2-D silicenes. The bonding in this new structure as well as its physical nature are fundamentally different from the covalent surface bonding that is widely accepted. From its structural characteristics, this polymorph arises from significant sp2-sp3 hybridization in the top layer that creates a 'faulted' honeycomb motif of Si atoms. This top layer has an unusual periodic p-orbital structure that can inter-digitate with the terminal bulk 'dangling bonds' to create a 2-D pi-bonded structure. This unusual bonding and new structure is important in understanding the nature of 2-D silicenes and 1-D honeycomb structures, as well as the conversion of the 1-D pi-bonded chains of the 2x1 structure to the 2-D pi-bonded 5x5 or 7x7 structures. Such extended pi-bonded structures can lead to non-covalent dispersion interactions that have not been accurately included in previous semiconductor surface calculations.