Elsevier

Applied Surface Science

Volume 257, Issue 15, 15 May 2011, Pages 6792-6798
Applied Surface Science

Investigation of the (√3 × √3)R30°-Cu2Si/Cu(1 1 1) surface alloy using DFT

https://doi.org/10.1016/j.apsusc.2011.02.128Get rights and content

Abstract

The electronic structure of the FCC, HCP and 2-fold bridge phases of the (√3 × √3)R30°-Cu2Si/Cu(1 1 1) surface alloy have been investigated using LCAO-DFT. Analysis of the total electron density, partial density-of-states (PDOS) and crystal orbital overlap population (COOP) curves for the system have shown a surprising similarity between the intra- and inter-layer Si–Cu bond for each phase. Low hybridization between the Si 3s and 3p orbitals results in a low directionality of the Si–Cu bond within each of phase. The Si 3s orbitals are shown to form covalent bonds with their surrounding Cu atoms whereas the Si 3p and 3d orbitals are shown to form combinations of covalent and metallic bonds. The Si–Cu interaction is shown clearly to extend to the second layer of the alloy in deference to previous studies of Si/Cu alloys.

Highlights

► Evident and surprising similarities between the Si–Cu interaction for each of these phases, despite differences in the surface-2nd layer registry and proven Si–Cu interactions between these two layers. ► Si states in these systems do not undergo significant hybridization, and the Si–Cu bonds lack directionality and form either covalent or metallic states. ► Significant distortions in the 2nd layer Cu 3d orbitals which are exactly compensated by bond length differences between the surface and 2nd layer, suggesting the masking of these effects in a simple work function analysis. ► Preliminary energetic analysis suggestive that boundary and mass transport effects dominate the formation of the stable mixed phase surface.

Introduction

Surface science studies of semiconductor–metal systems can serve as an effective building block in understanding commercial electronic material growth [1] and concurrently can further the understanding of industrial catalytic processes. The field is developed and extensive, with several decades of research contributing to our current understanding of these systems. The expressed interest in bi-metallic, and higher, alloyed surfaces arises from the fact that by controlling even the most basic growth parameters of these surfaces, such as stoichiometry and chemical composition, ‘tuning’ of the reactivity and electronic properties of the surface is seen experimentally. A fundamental, theoretical understanding of the reasons why particular components in the alloy produce different effects on the surface is a rigorous way of developing more effective and commercially more attractive materials and processes.

The (√3 × √3)R30°-Cu2Si/Cu(1 1 1) surface alloy has recently been investigated [2], [3] and has clearly shown that the alloy grows in 3 phases, with Si atoms occupying FCC, HCP and 2-fold bridge sites in ratio 25:25:50. The structure of the FCC, HCP and 2-fold bridge phases are shown in Fig. 1. These investigations are entirely unique within the field of metal–semiconductor interface formation, notably with their identification of multiple phase formation. Investigations of the electronic structures that form during semiconductor deposition on metal surfaces are very few in number. The Cu(1 1 0) + c(2 × 2)–Si system has been investigated using photoemission spectroscopy [4]. The study showed that the alloy electronic states favour an in-plane orientation enabled by hybridization of the Si 3p and Cu 3d states. Later computational studies of the Si/Cu(1 1 0) system [5] confirmed the assignment of the c(2 × 2) structure and identified the energetic preference of the Si ion cores to incorporate themselves in the surface layer rather than in on-surface sites, or bulk incorporation. Studies of Ag/Cu(1 1 0) [6] showed the formation of a substitutional alloy which undergoes a transition from 1D and 2D electronic structures at low (<0.4 ML) Ag coverages to 3D structures at high coverages. Some discussion showed that geometrical factors at much larger (>0.65 ML) coverages were accompanied by 1D and 2D electronic features. These features were assigned to hybridization between the Ag sp and Cu d states.

The effects of local binding geometry in bulk Si–Cu alloys were investigated by Magaud et al. [7] who identified the notable effects of Si p–Cu d hybridization in bulk Cu3Si. The relevance of this is the comparison of the form of Si bonding in bulk compared to, for example, common molecular forms where strong hybridization between the s and p states is seen. Other works on Al/Pd(1 0 0) [8] have identified that significant reconstruction of the surface layer coupled with incorporation of Al ion cores in the 2nd layer are required to form a stable structure. In balance, however, submission also exists which identify weak bonding effects between the alloy components – for example, Cu/W(0 0 1) [9].

The current therefore predominantly addresses the interactions between Si and Cu in each phase of the (√3 × √3)R30°-Cu2Si/Cu(1 1 1) surface alloy system. The significance of the Si–Cu interaction between ion cores in both the surface layer, and between ion cores in the surface and 2nd layers is elucidated. Further, some discussion of the Cu–Cu interaction in these phases is presented.

Section snippets

Computational details

The results presented in this paper were performed using the SIESTA method [10]. The pseudopotentials were generated according to the improved Troullier–Martins method [11] with non-linear core corrections [12]. Exchange-correlation was estimated using the GGA method [13]. A double-ζ split-valence basis set including polarization orbitals was used [14] and a single Kleinman–Bylander projector represented each angular momentum channel [15]. The simulations were performed using 3s and 3p orbitals

Results and discussion

The current work predominantly address the electronic structures of the (√3 × √3)R30°-Cu2Si/Cu(1 1 1) system rather than structural issues which have been previously published [2], [3]. One of the most powerful probes of total electronic structure is the work function change Δϕ during alloy formation. This change will contain all the electronic information about the surface change, albeit in a non-specific way.

The changes in work function Δϕ during formation of each of the FCC, HCP and 2-fold

Conclusions

The current work has investigated the FCC, HCP and 2-fold bridge phases of the (√3 × √3)R30°-Cu2Si/Cu(1 1 1) surface alloy. Surprising similarities between the Si–Cu interaction for each of these systems has been noticed. Analysis has revealed that the Si–Cu bonds lack directionality and can form either covalent or metallic states. Investigations into the role of the Cu 3d states in these systems have shown that the Cu3dxy and Cu3dx2y2 orbitals are oriented to lie the surface plane whilst the Cu3d

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