Converged properties of clean metal surfaces by all-electron first-principles calculations

All-electron full-potential linearized augmented plane-wave calculations of the surface energy, work function, and interlayer spacings of close-packed metal surfaces are presented, in particular, for the free-electron-like metal surfaces, Mg(0 0 0 1) and Al(1 1 1), and for the transition metal surfaces, Ti(0 0 0 1), Cu(1 1 1), Pd(1 1 1), and Pt(1 1 1). We investigate the convergence of the surface energy as a function of the number of layers in the slab, using the Cu(1 1 1) surface as an example. The results show that the surface energy, as obtained using total energies of the slab and bulk from separate calculations, converges well with respect to the number of layers in the slab. Obviously, it is necessary that bulk and surface calculations are performed with the same high accuracy. Furthermore, we discuss the performance of the local-density and generalized gradient approximations for the exchange-correlation functional in describing the various surface properties.     

Density functional theory investigation of the structure of SO2 and SO3 on Cu(1 1 1) and Ni(1 1 1)

Density functional theory (DFT) slab calculations, mainly using the generalised gradient approximation, have been used to investigate the minimum energy structures of molecular SO₂ and SO₃ on Cu(1 1 1) and Ni(1 1 1) surfaces. On Ni(1 1 1) the optimal local adsorption structures are in close agreement with experimental results for both molecular species obtained using the X-ray standing wavefield technique, although for adsorbed SO₂ the energetic difference between two alternative lateral positions of the lying-down molecule on the surface is marginally significant. On Cu(1 1 1) the results for adsorbed SO₂, in particular, were sensitive to the DFT functional used in the calculations, but in all cases failed to reproduce the experimentally-established preference for adsorption with the molecular plane perpendicular to the surface. This result is discussed in the context of previously published DFT results for these species adsorbed on Cu(1 0 0). The optimal geometry found for SO₃ on Cu(1 1 1) is similar to that on Ni(1 1 1), providing agreement with experiment regarding the molecular orientation but not the adsorption site.     

Simulation of Birefringence and Absorption in InGaAs-GaAs Multiple Quantum Well Acoustooptic Modulators Operating Near 980 nm

This paper presents the simulation of surface acoustic wave (SAW)-induced absorption coefficient and refractive index change in InGaAs-GaAs multiple quantum well (MQW) structures operating near 980 nm. The exciton problem is solved in two dimensional momentum space to include the non-axial effect due to strain induced valance band mixing and nonparabolicity. The optical absorption coefficient and refractive index changes near the band gap in the MQWs are calculated as a function of SAW power.     

Multifunctional ToF-SIMS: combinatorial mapping of gradient energy substrates

We present a simple method for chemical modification of chlorosilane self-assembled monolayers (SAMs) on Si surfaces by exposure to a gradient of UV-ozone radiation to create stable substrates with a range of contact angles (θ_H2O≈5–95°) and surface energies on a single substrate. These gradient energy substrates are developed to potentially generate libraries for combinatorial studies of thin film phenomenology, where a systematic variation of interfacial surface energy represents one of the significant parameters along one axis. The graded oxidation process presents a systematic variation of surface chemical composition. We have utilized contact angle measurements and time-of-flight secondary ion mass spectrometry (ToF-SIMS) to investigate this variation for a series of ions, among which are SiCH₃⁺, SiOH⁺ and COOH⁻. We show that the macroscopic measurements of surface free energy/contact angle correlate with the detailed analysis of surface chemistry (as assessed by ToF-SIMS) on these test substrates.     

ToF-SIMS analysis of a fluorocarbon-grafted PET with a gold cluster ion source

Cluster ions have been recognized as a superb primary species in time of flight secondary ion mass spectroscopy (ToF-SIMS) compared with monatomic primary ions, as they significantly enhance the secondary ion yields from bulk samples. Self-assembled monolayers provide an important system for studying the fundamental mechanism involved in the yield enhancement.We used a gold cluster ion source to analyze a new type of self-assembled monolayer: a fluorocarbon-grafted polyethylene terephthalate. In addition to the structure details, which helped to understand the grafting mechanism, ToF-SIMS analysis revealed that fluorocarbon secondary ion yield enhancements by cluster ions were due to the enhanced sputter efficiency. A larger information depth may also be expected from the enhancement. Both mathematical definitions of damage cross-section and disappearance cross-section were revisited under a new context. Another cross-section parameter, sputter cross-section, was introduced to differentiate the beam induced sputter process from damage process.     

The structure of monolayer SiO2 on Mo(1 1 2): A 2-D [Si-O-Si] network or isolated [SiO4] units?

In this letter, atomically resolved scanning tunneling microscopic (STM) images obtained from monolayer SiO₂/Mo(1 1 2) are presented. The results are consistent with a previously proposed structural model of isolated [SiO₄] units based on vibrational features observed by high-resolution electron energy loss spectroscopy (HREELS) and infrared reflection-absorption spectroscopy (IRAS), and oxygen species identified by ultra-violet photoemission spectroscopy (UPS). These results are inconsistent with a structural model that assumes a two-dimensional (2-D) [Si-O-Si] network. These data illustrate that a metal substrate, although coated with an oxide thin layer, can be directly imaged at the atomic-scale with STM.     

Controlled structure and density of “living” polystyrene brushes on flat silica surfaces

Thin layers of polystyrene were grown from surface-grafted nitroxide initiators via controlled “living” free radical polymerization. The “reactive” Langmuir-Blodgett deposition method allowed an effective control of the initiator layer density leading to PS brushes with different and high grafting density and stretching. The influence of the grafting density on the layer structure was studied. Comparison with theoretical predictions for monodispersed brushes in bad solvent was discussed. The thickness was found to vary linearly with molecular weight and the density dependence was shown using wetting measurements. Special features of controlled radical nitroxide polymerization from a surface were discussed. A direct comparison of the molecular weight and polydispersity between surface and bulk polymers was made by de-grafting the brushes into a toluene/HF solution. Finally, some evidence of a “surface Fischer” effect was shown from re-initiated layers. Received 20 December 2001     

Magnetic properties of the Cr(0 0 1) surface studied by spin-polarized scanning tunneling spectroscopy

The magnetic properties of the Cr(0 0 1) surface have been studied by spin-polarized scanning tunneling spectroscopy (SP-STS). Spatially resolved mapping of the spectroscopic dI/dU signal at an energy close to the spin-polarized Cr(0 0 1) surface state allows the confirmation of the topological antiferromagnetic order of the Cr(0 0 1) surface. It is shown that the presence of screw dislocations leads to the formation of domain walls which exhibit a width of 120–170 nm. A long-period modulation of the SP-STS signal was not observed indicating that the bulk spin-density wave is modified at the surface due to symmetry breaking.     

Site segregation in size-mismatched nanoalloys: Application to Cu-Ag

In order to determine the energetic driving forces for surface segregation in bimetallic clusters, we use a combined approach coupling numerical simulations within an N-body interatomic potential and a lattice-gas model. This approach, which has been used successfully to study both the superficial segregation in semi-infinite alloys and the intergranular segregation, allows us to determine the relative contributions of the three elementary driving forces for the different sites of the cluster surface (vertices, edges and facets) in both dilute limits for the Cu-Ag system. We show that the segregation hierarchy based on broken-bond arguments (preferential segregation to the vertex sites, less to edge sites, and least to facet sites) is not at all universal. In particular, unusual hierarchies are predicted when the sizes of the constituents are strongly different. Furthermore, we compare the segregation driving forces for cubo-octahedral and icosahedral clusters. They are similar for the vertex sites and edge sites, whereas they differ significantly for the sites of the triangular facets. The segregation of the species with the largest atomic radius (Ag) is indeed largely enhanced in the icosahedral structure due to dilations of the orthoradial distances.     

Surface free energy of CrNx films deposited using closed field unbalanced magnetron sputtering

CrN_x thin films have attracted much attention for semiconductor IC packaging molding dies and forming tools due to their excellent hardness, thermal stability and non-sticking properties (low surface free energy). However, few data has been published on the surface free energy (SFE) of CrN_x films at temperatures in the range 20-170 °C. In this study CrN_x thin films with CrN, Cr(N), Cr₂N (and mixture of these phases) were prepared using closed field unbalanced magnetron sputtering at a wide range of Cr⁺² emission intensity. The contact angles of water, di-iodomethane and ethylene glycol on the coated surfaces were measured at temperatures in the range 20-170 °C using a Dataphysics OCA-20 contact angle analyzer. The surface free energy of the CrN_x films and their components (e.g., dispersion, polar) were calculated using the Owens-Wendt geometric mean approach. The influences of CrN_x film surface roughness and microstructure on the surface free energy were investigated by atomic force microscopy (AFM) and X-ray diffraction (XRD), respectively. The experimental results showed that the lowest total SFE was obtained corresponding to CrN at temperature in 20 °C. This is lower than that of Cr(N), Cr₂N (and mixture of these phases). The total SFE, dispersive SFE and polar SFE of CrN_x films decreased with increasing surface temperature. The film roughness has an obvious effect on the SFE and there is tendency for the SFE to increase with increasing film surface roughness.