Molecular dynamics simulation of the (0 0 0 1) α-Al2O3 and α-Cr2O3 surfaces

A simple, rigid pair-potential model is applied to investigate the dynamics of the (0 0 0 1) α-Al₂O₃ and α-Cr₂O₃ surfaces using the molecular dynamics technique. The simulations employ a two-stage equilibration process: in the first stage the simulation-cell size is determined via the constant-stress ensemble, and in the second stage the equilibration of the size-corrected simulation cell is continued in the canonical ensemble. The thermal expansion coefficients of bulk alumina and chromia are evaluated as a function of temperature. Furthermore, the surface relaxation and mean-square displacement of the atoms versus depth into the slab are calculated, and their behaviour in the surface region analysed in detail. The calculations show that even moderate temperatures (∼400 °C) give rise to displacements of the atoms at the surface which are similar to the lattice mismatch between α-alumina and chromia. This will help in the initial nucleation stage during thin film growth, and thus facilitate the deposition of α-Al₂O₃ on (0 0 0 1) α-Cr₂O₃ templates.     

HREELS and LEED studies on Cu deposited on 1 × 1 reconstructed α-Fe2O3(0001) surfaces

High-resolution electron energy-loss spectroscopy (HREELS), low-energy electron diffraction, and X-ray photoelectron spectroscopy have been used to study clean 825 K-preannealed α-Fe₂O₃-1 × 1 (haematite) surfaces, an α-Fe₂O₃-(0001)-1 × 1 surface reconstructed with Fe₃O₄(111)-1 × 1 and to study Cu deposited on room-temperature surfaces of those. Three pronounced losses, at 47.5, 55.5 and 78.0 meV, of the surface phonons for the clean α-Fe₂O₃(0001) were observed. By deposition of copper, Cu---O vibrational features observed by HREELS indicate formation of a Cu(I) state for the very low coverages. Increased submonoloayer amounts of Cu result in clustering of the copper, leading for both the α-Fe₂O₃(0001)-1 × 1 and the reconstructed composite substrate surfaces to Cu(111) epitaxial growth.     

Luminescence properties of α-Al2O3 dosimetric crystals exposed to a high-current electron beam

The spectra of pulsed cathodoluminescence (PCL) and thermoluminescence (TL) in TLD-500 detectors, which were exposed to a strong beam from a pulsed electron accelerator, have been studied. Additional bands in the PCL spectrum and new peaks in the TL curves, which are due to impurity ions, have been revealed. Luminescence bands of F- and F⁺-centers cannot be used in the dosimetry of strong electron beams using TLD-500 detectors because of the saturation of dose dependence and the decrease in the TL yield. It is shown that high doses from these beams can be measured by recording TL in the luminescence band of impurity titanium ions.     

Self-regulated Ni cluster formation on the TiO2(1 1 0) terrace studied using scanning tunneling microscopy

We have studied the growth mode and morphology of Ni clusters on a TiO₂(1 1 0) surface with a wide terrace using scanning tunneling microscopy (STM) at a low coverage (less than 3 atoms nm⁻²). The Ni clusters are formed on the terrace at the low coverage of 0.2 atoms nm⁻². Their average dimensions are constant in three directions up to 1 atoms nm⁻². The Ni clusters have an oval shape with average sizes of 1.8 nm (along [0 0 1]) × 1.4 nm (along (in the [1 1 0] directions). Above the coverage of 1.0 atoms nm⁻², an increase in the cluster height occurs, retaining an almost constant lateral size. It is proposed that the interaction of the Ni cluster and the support surface regulates the Ni cluster size.     

Observation of the V2O5(001) surface using ambient atomic force microscopy

Constant force images of the V₂O₅(001) surface were recorded in ambient conditions with atomic force microscopy. All images exhibit the 11.5 Å × 3.5 Å. periodicity expected for a bulk terminated surface. However, images reveal differences from the ideal structure. The experimental results are interpreted in terms of preferential adsorption sites for water molecules. Because these sites are thought to influence the catalytic properties of the surface, their characterization is an important step towards understanding how the atomic-scale structure of a surface influences its properties.     

Growth of β-MnO2 films on TiO2(110) by oxygen plasma assisted molecular beam epitaxy

We have used oxygen plasma assisted MBE to grow epitaxial films of pyrolusite (β-MnO₂) on TiO₂(110) for thicknesses of one to six bilayers (BL). We define a bilayer to be a layer of Mn and lattice O and an adjacent layer of bridging O within the rutile structure. The resulting surfaces have been characterized in situ by reflection high-energy electron diffraction, low-energy electron diffraction, X-ray photoelectron spectroscopy and diffraction, and atomic force microscopy. Well-ordered, pseudomorphic overlayers form for substrate temperatures between 400 and 500°C. Mn–Ti intermixing occurs over the time scale of film growth (1 BL/min) for substrate temperatures in excess of 500°C. Films grown at 400–500°C exhibit island growth, whereas intermixed films grown at temperatures of 500–600°C are more laminar. 1 BL films grown at 450°C are more laminar than multilayer films grown at the same temperature, and form a well-ordered surface cation layer of Mn on the rutile structure with at most 10% indiffusion to the second cation layer.     

The adsorption of carbon monoxide on TiO2(110) supported palladium

Palladium overlayers deposited on TiO₂(110) by metal vapour deposition have been investigated using LEED, XPS and FT-RAIRS of adsorbed CO. Low coverages of palladium (<3 ML) deposited at 300 K adsorb CO exclusively in a bridged configuration with a band (B₁ at 1990 cm⁻¹) characteristic of CO adsorption on Pd(110) and Pd(100) surfaces. When annealed to 500 K, XPS and LEED indicate the nucleation of Pd particles on which CO adsorbs predominantly as a strongly bound linear species which we associate with edge sites on the Pd particles (L* band at 2085 cm⁻¹). Both bridged and linear CO bands are exhibited as increases in reflectivity at the resonant frequency, indicating the retention of small particle size during the annealing process. Palladium overlayers of intermediate coverages (10–20 ML) deposited at 300 K undergo some nucleation during growth, and adsorbed CO exhibits both absorption and transmission bands in the B₁ (1990 cm⁻¹) and B₂ (1940 cm⁻¹) regions. The latter is associated with the formation of Pd(111) facets. Highly dispersed Pd particles are produced on annealing at 500 K. This is evidenced by the dominance of transmission bands for adsorbed CO and a significant concentration of edge sites, which accommodate the strongly bound linear species at 300 K. Adsorption of CO at low temperature also allows the identification of the constituent faces of Pd and the conversion of Pd(110)/(100) facets to Pd(111) facets during the annealing process. High coverages of palladium (100 ML) produce only absorption bands in FT-RAIRS of adsorbed CO associated with the Pd facets, but annealing these surfaces also shows a conversion to Pd(111) facets. LEED indicates that at coverages above 10 ML, the palladium particles exhibit (111) facets parallel to the substrate and aligned with the TiO₂(110) unit cell, and that this ordering in the particles is enhanced by annealing.     

Study of the interactions between the overlayer and the substrate in the early stages of palladium growth on TiO2(1 1 0)

The interaction between palladium and the (1 1 0) surface of a TiO₂ single crystal and the electronic properties of the system were studied by means of photoelectron spectroscopy (core levels and valence band) and resonant photoemission for Pd coverage in the sub- and monolayer range. We performed the metal depositions at room temperature. Similarly to copper, platinum and rhodium, palladium does not reduce titanium, has metallic character already from a quite early deposition, grows with a 3D-island mode and the interactions between palladium and TiO₂ are very weak. Annealing treatments at 400 °C provoke a change in the morphology of the palladium clusters and the formation of islands characterized by a higher ratio between volume and area in contact with the substrate.     

The Fe3O4 origin of the “Biphase” reconstruction on α-Fe2O3(0 0 0 1)

The so-called Biphase termination on α-Fe₂O₃ has been widely accepted to be a structure with a 40 Å unit supercell composed of coexisting islands of Fe_1−xO and α-Fe₂O₃. Based on thermodynamic arguments and experimental evidence, including transmission electron diffraction, imaging, magnetic and spectroscopic information, it is found that the previously proposed structure model is inaccurate. The actual Biphase structure is instead a layered structure related to the reduction of α-Fe₂O₃ to Fe₃O₄. A model for the Biphase termination is proposed which does not contain islands of Fe_1−xO but instead consists of bulk α-Fe₂O₃ and a Fe₃O₄-derived overlayer. The proposed model is consistent with all current and previously reported experimental findings.     

Specific features of luminescence of radiation-colored α-Al2O3 single crystals

Results of a comparative study on specific features of luminescence of thermochemical and radiation-colored crystals of aluminum oxide have been described. It is shown that crystals containing oxygen vacancies of different origins have identical main optical properties. A vacancy or vacancy-impurity origin of deep traps has been assumed. Some specific features of thermoluminescence (TL), which are common for both types of crystals, such as the dependence of the TL output on the heating rate and the occupancy of deep traps described by the model of interactive trap system, have been established.     

Atomic force microscopy study on surface morphology of {0 0 1} faces of [MnHg(SCN)4(H2O)2]·2C4H9NO crystals

The growth morphologies of the {0 0 1} faces of [MnHg(SCN)₄(H₂O)₂]·2C₄H₉NO (MMTWD) crystals grown at 17 °C at a supersaturation of σ = 0.5 have been investigated by ex situ atomic force microscopy (AFM).Various spiral growth hillocks are described and discussed. Surface morphology changes as a result of dissolving the surface materials by absorbed moisture in air are also detected. The microcrystals are suggested to be as a result of the reconstruction of amorphous aggregates on the surfaces.     

Controlling metal/oxide interactions in bifunctional nanostructured model catalysts: Pd and BaO on Al2O3/NiAl(1 1 0)

We have investigated the structure and growth of Pd and BaO containing nanoparticles sequentially co-deposited on an ordered Al₂O₃/NiAl(1 1 0) by scanning tunneling microscopy (STM), and their interaction with CO and NO₂ by infrared reflection absorption spectroscopy (IRAS).Ba deposition and subsequent oxidation result in Ba_xAl_2yO_x+3y nanoparticles being formed which are characterized by high particle densities and nucleation both on regular terraces and at oxide defects. In contrast, Pd interaction with the model support is weaker and preferential nucleation occurs mainly at rotational domain boundaries and to a lesser extent at anti-phase domain boundaries. For subsequent co-deposition of Pd on preformed Ba_xAl_2yO_x+3y/Al₂O₃/NiAl(1 1 0), Pd nucleates at the Ba_xAl_2yO_x+3y nanoparticles and covers them. The reverse deposition sequence, i.e. subsequent Ba co-deposition and oxidation on preformed Pd/Al₂O₃/NiAl(1 1 0), leads to formation of small isolated Ba_xAl_2yO_x+3y nanoparticles without contact to Pd, together with large Pd crystallites modified by Ba_xAl_2yO_x+3y. The present results provide control over the degree of interaction between metal nanoparticles and oxide nanoparticles on a well-defined model catalyst and thus allow us to study effects related effects on the reactivity and catalytic behavior.     

Growth of Co nanoparticles on a nanostructured θ-Al2O3 film on CoAl(1 0 0)

We have investigated the growth of Co nanoparticles on θ-Al₂O₃/CoAl(1 0 0) by means of Auger electron spectroscopy (AES), high-resolution electron energy loss spectroscopy (EELS), low energy electron diffraction (LEED) and scanning tunneling microscopy (STM). Due to Volmer-Weber growth, Co forms particles with a mean diameter of approximately 2.5 nm and height of 0.8 nm. Even on the entirely covered oxide, there is no Ostwald ripening and Co particles stay structurally isolated. The nanoparticles exhibit a small size distribution and tend to form chains, as predetermined by the streak structure of the oxide template. For sufficient high coverages Co-core-CoO-shell nanoparticles may be evidenced, which is explained as a result of surfactant oxygen. The nanostructured particles may open the door to numerous applications, such as in catalysis and magnetoelectronic applications, where large areas of ordered nanodots are desired.     

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.     

Photo- and thermostimulated processes in α-Al2O3

We reported on the recombination processes determined by the release of electrons from defects connected with the dosimetric 430 K thermostimulated luminescence (TSL) peak as well as with the 260 K TSL peak. These TSL peaks appear in thermochemically reduced α-Al₂O₃ crystals containing hydrogen and emission of these TSL peaks corresponds to luminescence of the F-center. The X-ray exposure or UV excitation in the absorption band of F-centers at 6.0 eV of reduced α-Al₂O₃ crystals doped with acceptor impurities results in the appearance of a broad anisotropic complex absorption band in the spectral region 2.5–3.5 eV and in the appearance of a predominant TSL peak at 430 K. Above 430 K the above-mentioned broad absorption band disappears. Optical bleaching of the 2.5–3.5 eV band is accompanied by the disappearance of the 430 K TSL peak and results in F-center emission. The X-ray or UV excitation of reduced α-Al₂O₃ crystals with donor-type impurities results in the appearance of an anisotropic absorption band at 4.2 eV and the appearance of a dominant TSL peak at 260 K. Above 260 K the 4.2 eV absorption disappears and photostimulated luminescence (PSL) of the F-center recombination luminescence in the 4.2 eV region is no longer observed. Optical bleaching of the 4.2 eV absorption band is accompanied by the disappearance of the 260 K TSL peak. The successful use of reduced α-Al₂O₃ in dosimetry needs the optimization of the concentration of all components (acceptors, hydrogen, intrinsic defects) involved in the thermo- and photostimulated processes.     

Effect of α-Al2O3 on the properties of cold sprayed Al/α-Al2O3 composite coatings on AZ91D magnesium alloy

Composite coatings using pure Al powder blended with α-Al₂O₃ as feedstock were deposited on AZ91D magnesium alloy substrates by cold spray (CS). The content of α-Al₂O₃ in the feedstock was 25 wt.% and 50 wt.%, respectively. The effects of α-Al₂O₃ on the porosity, microhardness, adhesion and tensile strength of the coatings were studied. Electrochemical tests were carried out in neutral 3.5 wt.% NaCl solution to evaluate the effect of α-Al₂O₃ on the corrosion behavior of the coatings. The results showed that the composite coatings possessed lower porosity, higher adhesion strength and tensile strength than cold sprayed pure Al coating. The corrosion current densities of the composite coatings were similar to that of the pure Al coating and much higher than that of bare AZ91D magnesium alloy.     

One-dimensional structural and electronic properties of magnetite Fe3O4(1 1 0)

We study the structure and the electronic properties of the (1 1 0) surfaces of magnetite Fe₃O₄ thin films by scanning tunneling microscopy (STM) and spectroscopy (STS). The STM images show a surface reconstruction consisting of ridges along the direction. Based on atomically resolved STM images we present a model for the observed ridge reconstruction of the surface, in agreement with a bulk-truncated layer containing both octahedral and tetrahedral iron ions. The metallic and semiconductor-like shapes of the measured current-voltage (I-V) curves indicate a non-uniform segregation of magnesium through the film. The weak contrast between the tops and valleys of ridges measured in the STS current maps is attributed to tetrahedral and octahedral coordination at the tops and the valleys, respectively. This attribution is in agreement with the proposed structure model. We observe a contrast enhancement at a tip change accompanied by a corrugation enhancement. This tip change is induced by picking up material from the sample, resulting in a magnetic tip. Thus, the contrast enhancement is attributed to detection of spin polarized current.     

Adsorption and diffusion of a single Pt atom on γ-Al2O3 surfaces

Motivated to better understand the interactions between Pt and γ-Al₂O₃ support, the adsorption and diffusion of a single Pt atom on γ-Al₂O₃ was studied using density functional theory. Two different surface models with atoms of various coordination (3–5) were used, one derived from a defected spinel structure, and another derived from the dehydration of boehmite (AlOOH). Adsorption energies are similar for the two surfaces, about −2 eV for the most stable sites, and involve Pt binding to surface O atoms. An unusually strong trapping geometry whereby Pt moves into the surface was identified over the boehmite-derived surface. In all cases the surface transfers 0.2–0.3 e⁻ to the Pt atom. The bonding is explained as being a combination of charge transfer between the surface and Pt atom, polarization of the metal atom, and some weak covalent bonding. The similarity of the two surfaces is attributed to the similar local environments of the surface atoms, as corroborated by geometry analysis, density of states, and Bader charge analysis. Calculated activation barriers (0.3–0.5 eV) for the defected spinel surface indicate fast diffusion and a kinetic Monte Carlo model incorporated these barriers to determine exact diffusion rates and behavior. The kinetic Monte Carlo results indicate that at low temperatures (<500 K) the Pt atom can become trapped at certain surface regions, which could explain why the sintering process is hindered at low temperature. Finally we modeled the adsorption of Pt on hydrated surfaces and found adsorption to be weaker due to steric repulsion and/or decreased electron-donating ability of the surface.     

The local structure of SO2 and SO3 on Ni(1 1 1)

The normal incidence X-ray standing wave (NIXSW) technique, supported by X-ray photoelectron spectroscopy and near-edge X-ray absorption fine structure (NEXAFS), has been used to determine the local adsorption geometry of SO₂ and SO₃ on Ni(1 1 1). Chemical-state specific NIXSW data for coadsorbed SO₃ and S, formed by the disproportionation of adsorbed SO₂ after heating from 140 K to 270 K, were obtained using S 1s photoemission detection. For adsorbed SO₂ at 140 K the new results confirm those of an earlier study [Jackson et al., Surf. Sci. 389 (1997) 223] that the molecule is located above hollow sites with its molecular plane parallel to the surface and the S and O atoms in off-atop sites; corrections to account for the non-dipole effects in the interpretation of the NIXSW monitored by S 1s and O 1s photoemission, not included in the earlier work, remove the need for any significant adsorption-induced distortion of the SO₂ in this structure. SO₃, not previously investigated, is found to occupy an off-bridge site with the C_3v axis slightly tilted relative to the surface normal and with one O atom in an off-atop site and the other two O atoms roughly between bridge and hollow sites. The O atoms are approximately 0.87 Å closer to the surface than the S atom. This general bonding orientation for SO₃ is similar to that found on Cu(1 1 1) and Cu(1 0 0) both experimentally and theoretically, although the detailed adsorption sites differ.     

Structures of sulfur on TiO2(1 1 0) determined by scanning tunneling microscopy, X-ray photoelectron spectroscopy and low-energy electron diffraction

The temperature dependent adsorption of sulfur on TiO₂(1 1 0) has been studied with X-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy (STM), and low-energy electron diffraction (LEED). Sulfur adsorbs dissociatively at room temperature and binds to fivefold coordinated Ti atoms. Upon heating to 120°C, 80% of the sulfur desorbs and the S 2p peak position changes from 164.3±0.1 to 162.5±0.1 eV. This peak shift corresponds to a change of the adsorption site to the position of the bridging oxygen atoms of TiO₂(1 1 0). Further heating causes little change in S coverage and XPS binding energies, up to a temperature of 430°C where most of the S desorbs and the S 2p peak shifts back to higher binding energy. Sulfur adsorption at 150°C, 200°C, and 300°C leads to a rich variety of structures and adsorption sites as observed with LEED and STM. At low coverages, sulfur occupies the position of the bridging oxygen atoms. At 200°C these S atoms arrange in a (3×1) superstructure. For adsorption between 300°C and 400°C a (3×3) and (4×1) LEED pattern is observed for intermediate and saturation coverage, respectively. Adsorption at elevated temperature reduces the substrate as indicated by a strong Ti³⁺ shoulder in the XPS Ti 2p_3/2 peak, with up to 15.6% of the total peak area for the (4×1) structure. STM of different coverages adsorbed at 400°C indicates structural features consisting of two single S atoms placed next to each other along the [0 0 1] direction at the position of the in-plane oxygen atoms. The (3×3) and the (4×1) structure are formed by different arrangements of these S pairs.