DFT study of carbon monoxide adsorption on α-Al2O3(0001)

The adsorption of CO on α-Al₂O₃(0001) was studied using the DFT-GGA computational method and on α-Al₂O₃ powder experimentally by Infra red spectroscopy. The core and valence level regions of α-Al₂O₃(0001) single crystal surface were also studied experimentally. Ar ions sputtering of the surface results in a slight but reproducible decrease in the XPS O2p lines in the valence band regions due to preferential removal of surface (and near surface) O atoms. Core level XPS O1s and Al2p further confirmed oxygen depletion with an associated surface stoichiometry close to Al₂O_2.9. The adsorption energy of CO was computed and found equal to 0.52 eV for θ = 0.25, it decreased to 0.42 eV at θ = 1. The IR frequency of νCO was also computed and in all cases it was blue shifted with respect to gas phase CO. The shift, Δν, decreased with increasing coverage where it was found equal to 56 cm^? 1 for θ = 0.25 and decreased to 30 cm^? 1 for θ = 1. Structural analyses indicated that the change in the adsorption energy and the associated frequency shift is due to surface relaxation upon adsorption. Experimentally the adsorption of CO gave rise to one main IR peak at 2154 cm^? 1 at 0.3 Torr and above. Two far smaller peaks are also seen at lower pressures of 0.03–0.2 Torr at 2189 and 2178 cm^? 1. The isosteric heat of adsorption was computed for the IR band at 2154 cm^? 1 and was found equal to 0.2 eV which did not change with coverage in the investigated range up to θ = 0.6.     

Structure of the (0001) surface of α-Al2O3 from first principles calculations

Fully self-consistent ab initio calculations based on pseudopotentials are used to study the structure and energetics of the basal-plane surface of α-Al₂O₃. The calculated forces on the atoms are used to relax the atomic positions to equilibrium. It is shown that surface relaxations are very large and lead to a reduction of the surface energy by over a factor of two. The results support the validity of earlier work based on pair-interaction models.     

Pulsed laser deposition of Eu:Y2O3 thin films on (0001) α-Al2O3

This paper focuses on the preparation and characterization of crystalline thin films of rare-earth-doped sesquioxides (Y₂O₃, Lu₂O₃) grown by pulsed laser deposition on single-crystal (0001) sapphire substrates. X-ray diffraction measurements show that the films with thicknesses between 1 nm and 500 nm were highly textured along the 111 direction. Using Rutherford backscattering analysis, the correct stoichiometric composition of the films was established. The emission and excitation spectra of europium-doped films with a thickness 100 nm look similar to those of the corresponding crystalline bulk material, whereas films with a thickness 20 nm show a completely different emission behavior. PACS 68.55.Jk; 78.66.Nk; 81.15.F     

Oxygen plasma activation of Cr(CO)6 on α-Fe2O3(0001)

The chemistry of Cr(CO)₆ on the Fe₃O₄(111) surface termination of α-Fe₂O₃(0001) was explored using temperature programmed desorption (TPD), Auger electron spectroscopy (AES), static secondary ion mass spectrometry (SSIMS) and low energy electron diffraction (LEED) both with and without activation from an oxygen plasma source. No thermal decomposition of Cr(CO)₆ was detected on the surface in the absence of O₂ plasma treatment, with first layer molecules desorbing in TPD at 215 K from a close-packed overlayer. The interaction of first layer Cr(CO)₆ with the Fe₃O₄(111)-termination was weak, desorbing only ～ 30 K above the leading edge of the multilayer state. Activation of multilayer coverages of Cr(CO)₆ with the O₂ plasma source at 100 K resulted in complete conversion of the outer Cr(CO)₆ layers, presumably to a disordered Cr oxide film, with Cr(CO)₆ molecules near the surface left unaffected. Absence of CO or CO₂ desorption states suggests that all carbonyl ligands are liberated for each Cr(CO)₆ molecule activated by the plasma. AES and SSIMS both show that O₂ plasma activation of Cr(CO)₆ results in a carbon-free surface (after desorption of unreacted Cr(CO)₆). LEED, however, shows that the Cr oxide film was disordered at 600 K and likely O-terminated based on subsequent water TPD. Attempts to order the film at temperatures above 650 K resulted in dissolution of Cr into the α-Fe₂O₃(0001) crystal based on SSIMS, an observation linked to the Fe₃O₄(111) termination of the surface and not to the properties of α-Cr₂O₃/α-Fe₂O₃ corundum interface. Nevertheless, this study shows that O₂ plasma activation of Cr(CO)₆ is an effective means of depositing Cr oxide films on surfaces without accompanying carbon contamination.     

Photochemistry of methyl bromide on the α-Cr2O3(0001) surface

The photochemical properties of the Cr-terminated α-Cr₂O₃(0001) surface were explored using methyl bromide (CH₃Br) as a probe molecule. CH₃Br adsorbed and desorbed molecularly from the Cr-terminated α-Cr₂O₃(0001) surface without detectable thermal decomposition. Temperature programmed desorption (TPD) revealed a CH₃Br desorption state at 240 K for coverages up to 0.5 ML, followed by more weakly bound molecules desorbing at 175 K for coverages up to 1 ML. Multilayer exposures led to desorption at ~ 130 K. The CH₃Br sticking coefficient was unity at 105 K for coverages up to monolayer saturation, but decreased as the multilayer formed. In contrast, pre-oxidation of the surface (using an oxygen plasma source) led to capping of surface Cr³⁺ sites and near complete removal of CH₃Br TPD states above 150 K. The photochemistry of chemisorbed CH₃Br was explored on the Cr-terminated surface using post-irradiation TPD and photon stimulated desorption (PSD). Irradiation of adsorbed CH₃Br with broad band light from a Hg arc lamp resulted in both photodesorption and photodecomposition of the parent molecule at a combined cross section of ~ 10^? 22 cm². Photodissociation of the CH₃–Br bond was evidenced by both CH₃ detected in PSD and Br atoms left on the surface. Use of a 385 nm cut-off filter effectively shut down the photodissociation pathway but not the parent molecule photodesorption process. From these observations it is inferred that d-to-d transitions in α-Cr₂O₃, occurring at photon energies < 3 eV, do not significantly promote photodecomposition of adsorbed CH₃Br. It is unclear to what extent band-to-band versus direct CH₃Br photolysis play in CH₃–Br bond dissociation initiated by more energetic photons.     

First-principles study on the tensile strength and fracture of the Al-terminated stoichiometric α-Al2O3(0001)/Cu(111) interface

The first-principles tensile tests have been applied to the Al-terminated stoichiometric α-Al₂O₃(0001)/Cu(111) interface by using the ab initio pseudo-potential method based on the density-functional theory. Firstly, the Cu/Al and Cu/Cu interlayers have been examined by the rigid-type tensile test. The interlayer potential curves derived from the first-principles calculations are well fitted by the universal binding-energy relation (UBER) curves. The Cu–Al adhesion is weaker than the back Cu–Cu adhesion. Secondly, the relaxed-type tensile test has revealed the tensile strength and features of interfacial fracture. The ideal tensile strength is about 10?GPa, and the local Young's modulus is about 40?GPa, which means that the Cu/Al interface is quite weak and soft compared with the bulk regions and the O-terminated interface. The failure is initiated from the charge depletion region near the interfacial O atoms when the interlayer stretching exceeds about 30%, and the behaviour of electrons and ions indicates no strong Cu–O bond compared with substantial Cu–Al interactions. The present ab initio data are useful for the construction of effective interatomic potentials at the interface.     

First-principles study of the adhesive and mechanical properties of the O-terminated α-Al2O3(0001)/Cu(111) interfaces

Adhesive and mechanical properties of the O-terminated (O-rich) α-Al₂O₃(0001)/Cu(111) interface have been examined by the first-principles pseudopotential method. Strong Cu–O covalent and ionic interactions exist, such as Cu3d–O2p hybridization and substantial electron transfer from Cu to O, which result in larger adhesive energy, greater tensile strength and larger interfacial Young's moduli than the Al-terminated (stoichiometric) interface with electrostatic–image and Cu–Al hybridization interactions. Substantial effects of interfacial Cu–O coordination are also present. Changes in the interface electronic structure for cleavage have been examined. Cu–O interlayer potential curves have been analyzed using the universal binding energy relation and compared with Cu–Al and Cu–Cu curves, which is valuable for the development of effective interatomic potentials in large-scale simulations.     

Study of the Defect Structure and Crystal-Field Parameters of α-Al2O3:Yb3+

The methods currently used for studying the defect structure of laser host crystals doped with transition metal or rare-earth ions have several drawbacks or limitations. This study proposes an alternative approach for obtaining optimized impurity structures using molecular dynamics calculation in conjunction with the superposition model. This new approach is specifically applied to a system named α-Al₂O₃:Yb³⁺, in which the simulated defect structure is used to fit the superposition model parameters directly onto the observed energy levels. Such an approach provides predicted values of crystal-field parameters, Zeeman splitting g-factor, and hyperfine structure constants. Moreover, the C_3v site symmetry is found to be a good approximation for the actual C₃ site of Yb³⁺, as doped in an α-Al₂O₃ crystal.     

Synchrotron-Radiation Photoemission Study of Growth and Stability of Au Clusters on Rutile TiO2(110)-1×1

利用同步辐射高分辨光电子能谱研究了金团簇在部分还原TiO₂-(1×1)表面的生长和稳定性．价带谱实验结果观察到非常少量金团簇的沉积导致了Ti3+的3d峰完全消失,表明金团簇成核在TiO₂-(1×1)表面的氧缺陷位．Au4f芯电子光电子能谱实验结果证明了TiO₂-(1×1)表面氧缺陷位向金团簇转移电荷．还对比研究了化学剂量比和部分还原的TiO₂-(1×1)表面上金团簇的热稳定性．当金团簇尺寸相近时部分还原的TiO₂-(1×1)表面上金团簇要比化学剂量比的TiO₂-(1×1)面上金团簇稳定;在相同的表面上尺寸大的金团簇要比尺寸小的金团簇稳定．     

FT-IR Study of the Adsorption of Propane and Propene on V2O5/γ-Al2O3 Catalyst

It has been observed on the oxidized V₂O₅/γ-Al₂O₃ that C₃H₆ form alkoxides which were converted to acetone during the desorption of adsorbate phase at 373 K. C₃H₈ may form π-complexes on the reduced form of the same catalyst. However, the intensities of the bands in the ad-adsorption of C₃H₈ were very weak as compared with the case of C₃H₈ adsorption. Therefore, it was not reasonable to assign these bands clearly as any of the surface type species.     

FT-IR Study of the Adsorption of Propane and Propene on V2O5/γ-Al2O3 Catalyst

It has been observed on the oxidized V₂ O₅/γ-Al₂ O₃ that C₃H₆ form alkoxides which were converted to acetone during the desorption of adsorbate phase at 373 K. C₃ H₈ may form π-complexes on the reduced form of the same catalyst. However, the intensities of the bands in the adadsorption of C₃ H₈ were very weak as compared with the case of C₃ H₆ adsorption. Therefore, it was not reasonable to assign these bands clearly as any of the surface type species.     

Growth of ultrathin YBa2Cu3O7−x films on the SrTiO3 substrate

The growth of ultrathin (1.7–7.3 nm) YBa₂Cu₃O_7?x films on the SrTiO₃(100) substrate is investigated by the mean-energy ion scattering technique. It is found that the growth of islands proceeds according to the two-dimensional and three-dimensional models and depends on the growth conditions.     

The effect of annealing on the proton conductivity of Mg-doped α-Al2O3

In order to evaluate the effect of annealing treatment on the proton conductivity of ??-alumina, the electrical conductivity of Mg-doped polycrystalline ??-alumina kept at 1,873?K under various conditions of the surrounding atmosphere and then cooled in the furnace was measured in the temperature range 1,173?C1,473?K. The H⁺/D⁺ isotope effect on the electrical conductivity was also examined under a hydrogen atmosphere at 1,273?K. The protonic conductivity measured at 1,273?K increased with the increase in the activity of oxygen and water vapor in the annealing atmosphere at 1,873?K. It is considered that the solubility limit of magnesium ions in ??-alumina in equilibrium with the small amount of the spinel phase increased with the increase in the activity of oxygen and water vapor at 1,873?K. This enhanced amount of magnesium ions is frozen in a non-equilibrium state to 1,273?K and works as the enriched acceptor dopant for the incorporation of protons.     

Electron paramagnetic resonance and photoluminescence properties of α-Al2O3:Cr3+ phosphors

The red emitting Cr³⁺ activated α-Al₂O₃ powder phosphor has been prepared by easy combustion reactions from mixed metal nitrate reactants and urea with ignition temperatures of 500 °C. The as-synthesized powder was characterized by X-ray diffraction, scanning electron microscopy, and Fourier-transform infrared techniques. The X-ray diffraction pattern reveals that the phosphor crystallized in the hexagonal α-Al₂O₃ phase directly from the combustion reaction. The EPR spectrum exhibits an intense resonance signal with effective g value at g=3.33 along with a few weak resonance signals with effective g values at g=13.7, 2.34, 1.95, 1.49, and 1.26. The spin concentration (N) and its paramagnetic susceptibility (χ) have been evaluated. The excitation spectrum consists of two broad intense bands at 415 nm and 555 nm and are assigned to ⁴A_2g (F)→⁴T_1g (F) and ⁴A_2g (F)→⁴T_2g (F) transitions, respectively. The intense fluorescence peak around 691 nm is attributed to ²E _g →⁴A_2g transition of Cr³⁺ ion. By correlating EPR and optical data, the crystal field splitting parameter (Dq), Racah inter-electronic repulsion parameter (B) have been evaluated and discussed. The EPR and optical studies reveal that Cr³⁺ ions are occupying in Al³⁺ sites in octahedral coordination.     

Visible light induced photodesorption of NO from the α-Cr2O3(0001) surface

Nitric oxide chemistry and photochemistry on the Cr-terminated surface of α-Cr₂O₃(0001) were examined using temperature programmed desorption (TPD), sticking coefficient measurements and photodesorption. NO exposed to α-Cr₂O₃(0001) at 100 K binds at surface Cr cation sites forming a strongly bound surface species that thermally desorbs at 320–340 K, depending on coverage. No thermal decomposition was detected in TPD in agreement with previous results in the literature. Sticking probability measurements at 100 K indicated near unity sticking for NO up to coverages of ~ 1.3 ML, with additional adsorption with higher exposures at decreased sticking probability. These results suggest that some Cr cation sites on the α-Cr₂O₃(0001) surface were capable of binding more than one NO molecule, although it is unclear whether this was as separate NO molecules or as dimers. Photodesorption of adsorbed NO was examined for surface coverages below the 1 ML point. Both visible and UV light were shown to photodesorb NO without detectable NO photodecomposition. Visible light photodesorption of NO occurred with a greater cross section than estimated using UV light. The visible light photodesorption event was not associated with bandgap excitation in α-Cr₂O₃(0001), but instead was linked to excitation of a surface Cr^3 +–NO^? charge transfer complex. These results illustrate that localized photoabsorption events at surface sites with unique optical properties (relative to the bulk) can result in unexpected surface photochemistry.     

Electrical conductivity,diffusion of iron and the defect structure of α-Al2O3: Fe

A detailed defect model is developed for α-Al₂O₃:Fe accounting for conduction and diffusion at high temperatures as a function of iron concentration, oxygen pressure and temperature. This model involves single native and iron defects as well as triplets of (Fe_AlAl_iFe_Al), the latter dominating the defect structure at high Fe concentrations. Diffusion of Fe in A1₂O₃ is attributed to Fe_i^3.. The position of the Fe_Al' level is estimated.     

Comparative study of adsorption characteristics of Cs on the GaN(0001) and GaN(000) surfaces

The adsorption characteristics of Cs on GaN(0001) and GaN(000) surfaces with a coverage from 1/4 to 1 monolayer have been investigated using the density functional theory with a plane-wave ultrasoft pseudopotential method based on first-principles calculations.The results show that the most stable position of the Cs adatom on the GaN(0001) surface is at the N-bridge site for 1/4 monolayer coverage.As the coverage of Cs atoms at the N-bridge site is increased,the adsorption energy reduces.As the Cs atoms achieve saturation,the adsorption is no longer stable when the coverage is 3/4 monolayer.The work function achieves its minimum value when the Cs adatom coverage is 2/4 monolayer,and then rises with Cs atomic coverage.The most stable position of Cs adatoms on the GaN(000) surface is at H3 site for 1/4 monolayer coverage.As the Cs atomic coverage at H3 site is increased,the adsorption energy reduces,and the adsorption is still stable when the Cs adatom coverage is 1 monolayer.The work function reduces persistently,and does not rise with the increase of Cs coverage.     

Growth of CuO chains on Ag(110) surfaces

The (AgO) chains grown along the 〈001〉 direction on Ag(110) disappeared by the reaction with Cu atoms at room temperature, and new one-dimensional chains grew in the 〈110〉 direction. The STM images at different bias potentials suggest the growth of (CuO) chains in the 〈110〉 direction on the Ag(110) surface. The (CuO) chains on the Ag(110) surface disappeared by heating to 470 K, but they reappeared by exposing to O₂ at room temperature.