The adsorption and dissociation of O2 molecular precursors on Cu: the effect of steps

The adsorption and dissociation of dioxygen on Cu steps are studied using periodic self-consistent density functional theory (PW91-GGA) calculations. Cu steps are modeled with a Cu(2 1 1) surface. The results are compared with those on the flat Cu(1 1 1) surface. The adsorption of both atomic and molecular oxygen is enhanced on the stepped surface: the binding energy of atomic oxygen is −4.5 eV at its preferred site on the relaxed Cu(2 1 1) surface vs. −4.3 eV at its preferred site on the relaxed Cu(1 1 1) surface, and the binding energy of the molecular oxygen precursor is increased from ∼−0.6 to ∼−1.0 eV. Several possible O₂ dissociation paths at the edge of the Cu(2 1 1) step have been investigated. The activation energies range from 0.09 to 0.24 eV, comparable to a minimum activation energy of 0.20 eV found on Cu(1 1 1). However, compared to Cu(1 1 1) the paths on Cu(2 1 1) are stabilized in their entirety by the step by ∼0.5 eV in terms of initial state, transition state, and final state energies. The dissociation of O₂ precursors at the foot of the step is close to being barrier-less. Because of the small dissociation barrier on Cu(1 1 1), the effect of steps on O₂ dissociation is nevertheless not expected to be as pronounced as in other gas/metal systems.     

Hyperthermal scattering of Cs from Pt(1 1 1): the effect of image charge on the ion-surface energy transfer

We have studied the energy exchange between hyperthermal (5-100 eV) Cs⁺ projectiles and a Pt(1 1 1) surface by measuring the kinetic energy of the scattered ions. The scattering geometry was chosen to be in-plane with specular scattering angles, and the energy of the scattered ions was analyzed as functions of incidence energy and angle. For low incidence energy (<40 eV), the energy transfer to the Pt surface is substantially enhanced due to the attractive image charge force between Cs⁺ and the surface. The image charge effects are highlighted by the different energy transfer on Pt(1 1 1) and Si(1 1 1) surfaces. Analysis of the experimental results using two- and three-dimensional theoretical models revealed a well depth of 1 eV for the image charge potential. Hyperthermal Cs⁺ ions scatter from Pt(1 1 1) predominantly via double collisions with Pt atoms, though the scattering phenomena are insensitive to the impact site at the surface.     

First-principles study on the half-metallicity of zinc-blende CrP(1 1 0) surface

We have investigated the half-metallicity and magnetism at the (1 1 0) surface of CrP by using the all-electron full-potential linearized augmented plane wave (FLAPW) method within the generalized gradient approximation (GGA). From the calculated local density of states (LDOS), we found that the (1 1 0) surface of CrP preserves the half-metallicity, but the band gaps (∼1.1 eV) of the minority states for the surface Cr and P atoms are much reduced from the bulk value (∼1.9 eV). The magnetic moment of the P is coupled antiferromagnetically to that of the Cr. The magnetic moment of surface Cr atom is calculated to be 3.31μ_B which is increased by 10% compared to the bulk value, 3.00μ_B.     

On ultra-thin oxide/Si and very-thin oxide/Si structures prepared by wet chemical process

The properties of ultra-thin oxide/Si and very-thin oxide/Si structures prepared by wet chemical oxidation in nitric acid aqueous solutions (NAOS) and passivated in HCN aqueous solutions were investigated by electrical, optical and structural methods. n- and p-doped (1 0 0) crystalline Si substrates were used. There were identified more types of interface defect states in dependence on both post-oxidation treatment and passivation procedure. On samples prepared on n-type Si, continuous spectrum of defect states of 0.05-0.2 eV range and discrete defect traps, ∼E_CB − 0.26 eV and ∼E_CB − 0.39 eV, were found. All mentioned defects are related with various types of Si dangling bonds and/or with SiO_x precipitates. Post-metallization annealing of investigated MOS structures reduced the interface defect density and suppressed the leakage currents. It did not change spectral profile of interface defect states in the Si band gap. In addition, there are presented following two optical phenomena: relation between amplitude of photoluminescence signal of NAOS samples and parameters of chemical oxidation process and quantum confinement effect observed on samples containing Si grains of size less as ∼2 nm.     

Kinetics of residual gas adsorption on Ge(1 1 1) surface in low-energy electron backscattering

Low-energy (0.4-1.2 eV) electron backscattering is applied for the investigation of kinetics of residual gas adsorption effect on the concentration and energy positions of surface electron states of Ge(1 1 1) surface. Chemosorption of residual gas molecules on Ge(1 1 1) at P ∼ 10⁻⁷ Pa and room temperature is shown to be most active during the first 48 h. Low concentration of dangling valence bonds on the reconstructed Ge(1 1 1) (2 × 8) surface is shown to determine its low activity to chemosorption.     

Probability of ionization of sputtered particles as a function of their energy: Part I: Negative Si ions

In this study we have investigated how the probability of ionization of sputtered Si atoms to form negative ions depends on the energy of the atoms. We have determined the ionization probability from experimental SIMS energy distributions using a special experimental technique, which included de-convolution of the energy distribution with an instrumental transmission function, found by separate measurements.We found that the ionization probability increases as a power law ∼E^0.677 for particles sputtered with energies of 0-10 eV, then becomes a constant value (within the limits of experimental error) for particles sputtered with energies of 30-100 eV. The energy distributions of Si⁻ ions, measured under argon and cesium ion sputtering, confirmed this radical difference between the yields from low and high-energy ions.To explain these results we have considered ionization mechanisms that are different for the low energy atoms (<10 eV) and for the atoms emitted with higher energy (>30 eV).     

The wettability of polytetrafluoroethylene and polymethylmethacrylate by aqueous solutions of Triton X-100 and short chain alcohol mixtures

Measurements of advancing contact angles (θ) were carried out for aqueous solutions of Triton X-100 (TX-100) and methanol and ethanol mixtures at constant TX-100 concentration equal to 1 × 10⁻⁷, 1 × 10⁻⁶, 1 × 10⁻⁵, 1 × 10⁻⁴, 6 × 10⁻⁴ and 1 × 10⁻³ M, respectively, on polytetrafluoroethylene (PTFE) and polymethylmethacrylate (PMMA). Using measured contact angle values the relationships between cos θ, adhesion tension and surface tension of the solutions were determined, and on their basis the critical surface tension of PTFE and PMMA wetting was calculated. The obtained average value of the critical surface tension of PTFE wetting is lying in the range of the PTFE surface tension values which can be found in the literature, while for PMMA it is even lower than the Lifshitz-van der Waals component of its surface tension. From the relationship between the adhesion and surface tension and Lucassen-Reynders equation it results that in the case of PTFE the adsorption at the PTFE-solution and solution-air interfaces is the same, which was confirmed by a linear relationship between the cos θ and 1/γ_LV and intercept on cos θ axis equal to −1. However, for PMMA the adsorption of the surface active agents at solution-air interface is higher than at PMMA-solution. Using the values of the contact angle the values of the adhesion work of solution to the PTFE and PMMA surface were also determined, which are constant for PTFE, but for PMMA decrease with alcohol concentration increase. Next, using the contact angle values in the Young equation, the PTFE(PMMA)-solution interface tension was also calculated. The obtained values of PTFE-solution interface tension were compared with those evaluated from the Szyszkowski, Connors and Fainerman and Miller equations, and good agreement between these values was observed for all series of TX-100 and alcohol mixtures at a low alcohol concentration.     

TL and PL studies on defect-assisted green luminescence from doped strontium sulfide phosphor

Defect-assisted luminescence of Pr³⁺-doped SrS has been investigated and reported in this paper. The polycrystalline sample of phosphor was prepared by conventional solid-state reaction method and checked for crystallization and phase by X-ray diffraction study. The thermally stimulated luminescence studies of the phosphor samples with various activator concentrations, irradiated by a blacklight source, are conducted and show a broad single peak around 365-382 K. Computerized glow curve deconvolution tool is used to evaluate the effective trapping parameters and suggests quasi-continuous distribution of traps in the range of 0.5−0.9 eV. A critical survey on the application of first-order kinetics in the present phosphor is undertaken. Photoluminescence studies reveal three excitation bands at 287, 314, 355 nm and defect-related emission at 517, 494 nm for two concentrations of activator atoms in the present phosphor. The 314-355 nm broad excitation bands correspond to a charge transfer transition of Pr³⁺-S²⁻.     

Surface electron accumulation in indium nitride layers grown by high pressure chemical vapor deposition

Surface termination and electronic properties of InN layers grown by high pressure chemical vapor deposition have been studied by high resolution electron energy loss spectroscopy (HREELS). HREEL spectra from InN after atomic hydrogen cleaning show N-H termination with no indium overlayer or droplets and indicate that the layer is N-polar. Broad conduction band plasmon excitations are observed centered at 3400 cm⁻¹ in HREEL spectra with 7 eV incident electron energy which shift to 3100 cm⁻¹ when the incident electron energies are 25 eV or greater. The shift of the plasmon excitations to lower energy when electrons with larger penetration depths are used is due to a higher charge density on the surface compared with the bulk, that is, a surface electron accumulation. These results indicate that surface electron accumulation on InN does not require excess indium or In-In bonds.     

Surface mass diffusion and step stiffness on an anisotropic surface; Mo(0 1 1)

Results of step fluctuation experiments for Mo(0 1 1), using low-energy electron microscopy, are re-examined using recently developed procedures that offer accurate coefficients of surface mass diffusion. By these means, surface diffusion D_s is documented at T/T_m ∼ 0.5, while the crossover to relaxation driven by bulk vacancy diffusion is inferred for T/T_m ∼ 0.6. Here, T_m is the melting temperature T_m = 2896 K. We obtain D_s = 4 × 10⁻⁴ exp(−1.13 eV/k_BT) cm²/s for the temperature interval 1080-1680 K. Possible indications of diffusion along step edges appear for T/T_m ∼ 0.4. The same measurements of step fluctuation amplitudes determine also the step stiffness, which by symmetry is anisotropic on Mo(0 1 1). It is shown that three independent procedures yield mutually consistent step stiffness anisotropies. These are (1) step fluctuation amplitudes; (2) step relaxation rate anisotropies; and (3) the observed anisotropies of islands in equilibrium on the Mo(0 1 1) surface. The magnitude of the step stiffness obtained from step edge relaxation is consistent with earlier measurements that determine diffusion from grain boundary grooving.     

The wettability of polytetrafluoroethylene and polymethylmethacrylate by aqueous solutions of Triton X-100 and propanol mixtures

Measurements of advancing contact angles (θ) were carried out for aqueous solutions of Triton X-100 (TX-100) and propanol mixtures at constant TX-100 concentration equal to 1 × 10⁻⁷, 1 × 10⁻⁶, 1 × 10⁻⁵, 1 × 10⁻⁴, 6 × 10⁻⁴ and 1 × 10⁻³ M, respectively, on polytetrafluoroethylene (PTFE) and polymethyhmethacrylate (PMMA). Using obtained results the changes of cosθ and adhesional tension against surface tension of all series of aqueous solutions of TX-100 and propanol mixtures (γ_LV) for PTFE and PMMA surfaces were shown. On the basis of these changes it was deduced that adsorption of TX-100 and propanol mixtures at PTFE-solution and solution-air interfaces is the same but the adsorption of TX-100 and propanol mixtures at solution-air interface is considerably higher than at PMMA-solution one. In the case of PTFE this conclusion was confirmed by relationship between cosθ and the reciprocal of the surface tension of solution. Extrapolation of the relationships between cosθ and/or adhesional tension and the surface tension of solutions to the points corresponding to the cosθ = 1 and adhsional tension equal to the surface tension of solution, the critical surface tension of PTFE and PMMA wetting was determined. The average values of critical surface tension of wetting determined from these relationships for PTFE are lying in the range of its surface tension values determined from contact angles of different kinds of liquids, which can be find in the literature, but for PMMA are considerably lower than the surface tension. The double value of the critical surface tension of PTFE wetting is equal to adhesion work of the solution to its surface and for PMMA there is not any correlation between these magnitudes.Using the measured values of the contact angles and Young equation the PTFE(PMMA)-aqueous solution interfacial tension was determined. The interfacial tension values of PTFE-aqueous solution were also calculated from the Fainerman and Miller equation in which the correcting parameter of nonideality of the surface monolayer was introduced and compared to those obtained from Young equation. From this comparison it results that the changes of PTFE-solution interface tension as a function of propanol concentration can be described by the Fainerman and Miller equation.     

Interdiffusion of adsorbed Pb and Bi on Cu(1 0 0)

The impingement and interdiffusion of adsorbed Pb and Bi layers spreading from separated 3D pure bulk sources on Cu(1 0 0) has been studied, at T = 513 K, by in situ scanning Auger microscopy. When the leading edges of the pure Pb and Bi diffusion profiles impinge, they both consist of low-coverage lattice gas surface alloyed phases. In these low-coverage phases, Pb displaces surface alloyed Bi and the point of intersection of the profiles drifts towards the Bi source. These features lead to the conclusion that Pb atoms are more strongly bound at surface alloyed sites in Cu(1 0 0) than Bi atoms. Once the total coverage (Pb + Bi) on the substrate reaches about one monolayer, Pb and Bi are dealloyed from the substrate, and the interdiffusion profiles become essentially symmetric. Pb and Bi mix in all proportions, with an interdiffusion coefficient of ∼10⁻¹³ m²/s. This is considerably smaller than the self-diffusion coefficients previously observed for pure Pb and Bi in their respective high-coverage phases, indicating that the mechanism of interdiffusion is different from that of self-diffusion. As interdiffusion proceeds, the point of intersection of the Pb and Bi profiles reverses its drift direction, leading to the conclusion that binding of Bi atoms to the Cu(1 0 0) substrate is stronger than that of Pb atoms in the highest-coverage surface dealloyed layers.     

Influence of ferroelectric polarization on the energetics of the reaction of 2-fluoroethanol on BaTiO3

The influence of ferroelectric polarization on the reaction of 2-fluoroethanol on ferroelectric BaTiO₃ thin films was characterized. 2-Fluoroethanol was found to absorb dissociatively on the BaTiO₃ surface to form an alkoxide that reacts upon heating to produce acetaldehyde, ethylene, and adsorbed fluorine atoms which remain on the surface. Temperature programmed desorption (TPD) studies showed that the activation energy for the production of the acetaldehyde product was a function the orientation of the ferroelectric dipoles with an ∼4 kJ mol⁻¹ higher value on the c+ termination relative to the c− termination.     

Characterization of deep level defects in sublimation grown p-type 6H-SiC epilayers by deep level transient spectroscopy

In this study deep level transient spectroscopy has been performed on boron–nitrogen co-doped 6H-SiC epilayers exhibiting p-type conductivity with free carrier concentration (N_A–N_D)∼3×10¹⁷ cm⁻³. We observed a hole H₁ majority carrier and an electron E₁ minority carrier traps in the device having activation energies E_v+0.24 eV, E_c −0.41 eV, respectively. The capture cross-section and trap concentration of H₁ and E₁ levels were found to be (5×10⁻¹⁹ cm², 2×10¹⁵ cm⁻³) and (1.6×10⁻¹⁶ cm², 3×10¹⁵ cm⁻³), respectively. Owing to the background involvement of aluminum in growth reactor and comparison of the obtained data with the literature, the H₁ defect was identified as aluminum acceptor. A reasonable justification has been given to correlate the E₁ defect to a nitrogen donor.     

Characterization of defects introduced in Sb doped Ge by 3 keV Ar sputtering using deep level transient spectroscopy (DLTS) and Laplace-DLTS (LDLTS)

We have used deep level transient spectroscopy (DLTS), and Laplace-DLTS to investigate the defects created in antimony doped germanium (Ge) by sputtering with 3 keV Ar ions. Hole traps at E_V+0.09 eV and E_V+0.31 eV and an electron trap at E_C−0.38 eV (E-center) were observed soon after the sputtering process. Room temperature annealing of the irradiated samples over a period of a month revealed a hole trap at E_V+0.26 eV. Above room temperature annealing studies revealed new hole traps at E_V+0.27 eV, E_V+0.30 eV and E_V+0.40 eV.     

Dry etching of CuCrO2 thin films

Highly conducting films of p-type CuCrO₂ are attractive as hole-injectors in oxide-based light emitters. In this paper, we report on the development of dry etch patterning of CuCrO₂ thin films. The only plasma chemistry that provided some chemical enhancement was Cl₂/Ar under inductively coupled plasma conditions. Etch rates of ∼500 Å min⁻¹ were obtained at chuck voltages around −300 V and moderate source powers. In all cases, the etched surface morphologies were improved relative to un-etched control samples due to the smoothing effect of the physical component of the etching. The threshold ion energy for the onset of etching was determined to be 34 eV. Very low concentrations (≤1 at.%) of residual chlorine were detected on the etched surfaces but could be removed by simple water rinsing.     

A study of interface characteristics in HfAlO/p-Si by deep level transient spectroscopy

Deep level transient spectroscopy (DLTS) and high-frequency capacitance-voltage (HF-CV) measurement are used for the investigation of HfAlO/p-Si interface. The so-called “slow” interface states detected by HF-CV are obtained to be 2.68 × 10¹¹ cm⁻². Combined conventional DLTS with insufficient-filling DLTS (IF-DLTS), the true energy level position of interfacial traps is found to be 0.33 eV above the valance band maximum of silicon, and the density of such “fast” interfacial traps is 1.91 × 10¹² cm⁻² eV⁻¹. The variation of energy level position of such traps with different annealing temperatures indicates the origin of these traps may be the oxide-related traps very close to the HfAlO/Si interface. The interfacial traps’ passivation and depassivation effect of postannealing in forming gas are shown by comparing samples annealed at different temperatures.     

Studies on CdTe films deposited by pulsed laser deposition technique

Polycrystalline cadmium telluride films were successfully deposited on glass substrates by ablating a CdTe target by pulsed Nd–YAG laser. Microstructural studies indicated an increase in the average crystallite size from 15 nm to ∼50 nm with the increase in substrate temperature during deposition. The films deposited here were slightly tellurium rich. X-ray diffraction pattern indicated that the films deposited at 300 K had wurtzite structure while those deposited above 573 K were predominantly of zinc blende structure. Residual strain in the films deposited at 300 K was quite low as compared to those deposited at higher temperatures. PL spectra of all the CdTe films were dominated by a strong peak at ∼921 nm (∼1.347 eV) followed by a low intensity peak at ∼863 nm (∼1.438 eV). Characteristics Raman peaks for CdTe indicated a peak at ∼120 cm⁻¹ followed by peaks located at ∼140 cm⁻¹ and 160 cm⁻¹.     

Active oxidation: Silicon etching and oxide decomposition basic mechanisms using density functional theory

The etching of silicon atom from the Si(1 0 0)-p(2 × 2) surface, i.e. the desorption of SiO molecules from this surface, either clean or pre-oxidized, is investigated at the density functional theory level. The reaction paths for desorption are given as a function of the initial oxidation state of the extracted silicon atom. The associated activation energies and the atomic configurations are discussed. Particularly, it is shown that desorption of SiO molecules takes place during conventional thermal oxide growth (∼2 eV activation) via non-oxidized silicon atoms. Further SiO extraction mechanisms of higher silicon oxidation states required higher temperatures. In particular, doubly oxidized silicon atoms (Si²⁺) are able to decompose with an activation of ∼4 eV which corresponds to the actual temperature where decomposition of oxides is observed. This confirms the statement that decomposition of oxide layer nucleates at the interface with silicon where Si²⁺ has been detected thanks to XPS experiment.     

Hydroxylation-induced modifications of the Al2O3/NiAl(0 0 1) surface at low water vapour pressure

STM, STS, LEED and XPS data for crystalline θ-Al₂O₃ and non-crystalline Al₂O₃ ultra-thin films grown on NiAl(0 0 1) at 1025 K and exposed to water vapour at low pressure (1 × 10⁻⁷-1 × 10⁻⁵ mbar) and room temperature are reported. Water dissociation is observed at low pressure. This reactivity is assigned to the presence of a high density of coordinatively unsaturated cationic sites at the surface of the oxide film. The hydroxyl/hydroxide groups cannot be directly identify by their XPS binding energy, which is interpreted as resulting from the high BE positions of the oxide anions (O_1s signal at 532.5-532.8 eV). However the XPS intensities give evidence of an uptake of oxygen accompanied by an increase of the surface coverage by Al³⁺ cations, and a decrease of the concentration in metallic Al at the alloy interface. A value of ∼2 for the oxygen to aluminium ions surface concentration ratio indicates the formation of an oxy-hydroxide (AlO_xOH_y with x + y ∼ 2) hydroxylation product. STM and LEED show the amorphisation and roughening of the oxide film. At P(H₂O) = 1 × 10⁻⁷ mbar, only the surface of the oxide film is modified, with formation of nodules of ∼2 nm lateral size covering homogeneously the surface. STS shows that essentially the valence band is modified with an increase of the density of states at the band edge. With increasing pressure, hydroxylation is amplified, leading to an increased coverage of the alloy by oxy-hydroxide products and to the formation of larger nodules (∼7 nm) of amorphous oxy-hydroxide. Roughening and loss of the nanostructure indicate a propagation of the reaction that modifies the bulk structure of the oxide film. Amorphisation can be reverted to crystallization by annealing under UHV at 1025 K when the surface of the oxide film has been modified, but not when the bulk structure has been modified.